Synthesis of functionalized thietanes via electrophilic carbenoid-induced ring expansion of thiiranes with sulfonium acylmethylides as carbene precursors

Article abstract of DOI:10.1021/acs.joc.9b01152

Various functionalized thietanes were prepared from thiiranes via an electrophilic ring expansion with rhodium carbenoids as electrophiles generated from safe and readily accessible dimethylsulfonium acylmethylides. The reaction appears to proceed through electrophilic metallocarbenoid-induced activation of thiiranes, nucleophilic ring-opening of the activated thiiranes with dimethyl sulfide as a transient nucleophile, and nucleophilically intramolecular cyclization. The Umpolung from the nucleophilic ylides to the electrophilic carbenoids plays an important role in both the activation and ring opening of thiiranes and subsequent cyclization. The current method provides a new strategy for the efficient preparation of functionalized thietanes from readily available thiiranes.

Full text of DOI:10.1021/acs.joc.9b01152

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Article
Synthesis of Functionalized Thietanes via Electrophilic
Carbenoid-Induced Ring Expansion of Thiiranes with
Sulfonium Acylmethylides as Carbene Precursors
Jun Dong, Hongguang Du, and Jiaxi Xu
J. Org. Chem., Just Accepted Manuscript • DOI: 10.1021/acs.joc.9b01152 • Publication Date (Web): 12 Aug 2019
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The Journal of Organic Chemistry
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Synthesis of Functionalized Thietanes via Electrophilic
Carbenoid-Induced Ring Expansion of Thiiranes with
Sulfonium Acylmethylides as Carbene Precursors
Jun Dong, Hongguang Du, and Jiaxi Xu*
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State Key Laboratory of Chemical Resource Engineering, Department of Organic Chemistry, College
of Chemistry, Beijing University of Chemical Technology, Beijing 100029, People’s Republic of
China
Supporting Information
ABSTRACT: Various functionalized thietanes were prepared from thiiranes via an electrophilic ring
expansion with rhodium carbenoids as electrophiles generated from safe and readily accessible
dimethylsulfonium acylmethylides. The reaction appears to proceed through electrophilic metallocarbenoid-
induced activation of thiiranes, nucleophilic ring-opening of the activated thiiranes with dimethyl sulfide as a
transient nucleophile, and nucleophilically intramolecular cyclization. The umpolung from the nucleophilic
ylides to the electrophilic carbenoids plays an important role in both the activation and ring-opening of
thiiranes, and subsequent cyclization. The current method provides a new strategy for the efficient preparation
of functionalized thietanes from readily available thiiranes.
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Simultaneously, sulfur ylides can also act as the precursors
INTRODUCTION
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of electrophilic metallocarbenoids after an umpolung
conversion with transition metal catalysts.16 However, the most
recent application of this type of metallocarbenoids is only
limited to the insertion of acidic XH (X = C, N, O, S) bonds
and cyclopropanations.11a,17 The development of reactions
involving sulfur-ylide-derived metallocarbenoids for a wide
range of applications is in high demand since the method with
ylides as the carbenoid precursors can offer some advantages of
safety, stability, and easy operation over that with diazo
compounds as carbenoid precursors.11a,18 Most sulfur ylides are
safe in large-scale preparation, crystallizable, and bench-
stable.18 Thus, it is possible to replace diazo compounds with
sulfur ylides in metallocarbenoid reactions.19
Thietanes are pharmaceutically important cores or moieties
of some biological compounds, such as thietanose nucleosides,1
and spiroannulated glycothietane nucleosides as the
thiaanalogues of antiviral (anti-HIV and HSV) oxetanocin A
and their conformationally restricted analogues,2 the thia
derivatives of docetaxel, D-ring modified anticancer drug
taxoids,3 and thiathromboxane A2 (Figure 1).4
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The carbenoid-induced electrophilic ring expansions of four-
membered heterocycles into five-membered heterocycles have
been realized in limited cases.20 The transformation occurs
because the ring strain of the four-membered ring releases.
Although the reactions of three-membered heterocycles
containing heteroatoms (O, N, and S) with metallocarbenoids
generated from diazo compound precursors have been explored,
six-membered heterocyclic products were obtained
accompanied by the removal of heteroatoms during the
reactions.21,22 Because the four-membered rings are still
strained rings, it is certain difficult transformation from three-
membered rings directly to four–membered rings through a ring
expansion, compared with other larger rings.21b,22 Until 2017,
the first example was reported on the strained aziridines with
electrophilic one-carbon sources to trigger a ring-opening and
ring-closing cascade to yield azetidines.23 However, the
reaction was applied only in the designed special bicyclic
methyleneaziridines.
Figure 1. Pharmaceutically Important Compounds with the
Thietane Ring as Crucial Cores.
Thietanes also serve as important intermediates in organic
synthesis for the preparation of sulfur-containing compounds
and thiaheterocycles.5 Although thietanes have been widely
applied in organic synthesis and medicinal chemistry, their
synthetic methods are very limited to date.6 One traditional
route is intermolecular double substitutions of 1,3-
dihaloalkanes,1b sulfonates of 3-haloalkan-1-ols, or disulfonates
of alkane-1,3-diols with sodium sulfide.1a Another alternative
method is [2+2] photocycloaddition, Paterno-Büchi like
cycloaddition, of alkenes and thiocarbonyl compounds,7
especially cyclic thioimides, to afford spirocyclic
amidothietanes.8 Alkylidenethietanes have been prepared via
the amine-catalyzed tunable formal [2+2] cycloadditions of
allenoates and dithioesters.9 3-Substituted thietanes have been
prepared through the reactions of (1-chloroalkyl)thiiranes,
especially epithiochlorohydrin, and various nucleophiles.10
Sulfur ylides (sulfonium and sulfoxonium methylides) have
been used as universal synthetic precursors for various chemical
transformations.11 They have been widely applied as sources of
methylene synthons to synthesize small cyclic compounds
through a nucleophilic attack and intramolecular ring closure
sequence, for example, syntheses of oxiranes, aziridines, and
cyclopropanes with electrophilic aldehydes, imines, and
enones;12 and preparations of azetidines,13 oxetanes,14 and
15
thietanes with strained aziridines, oxiranes, and thiiranes as
Scheme 1. Synthesis of Thietanes from Thiiranes
electrophiles, respectively. However, the nucleophilic ring
expansions have been applied in only limited cases. In most
cases, only dimethylsulfonium and/or sulfoxonium methylides
have been used as nucleophiles in the nucleophilic ring
expansions for the preparation of four-membered
heterocycles.13a,13b,14,15 When the methods were extended to
functionalized sulfur ylides, especially with electron-
withdrawing groups, the ring expansion generally did not occur,
except for the reactions of the aziridines bearing electron-
withdrawing substituents with dimethylsulfonium and
sulfoxonium 2-phenyl-2-oxoethylide ylides.13c,13d
Considering that the carbon atoms of thiiranes are less
electrophilic due to less polar CS bond (similar
electronegativities of sulfur and carbon), unfavorably reacting
with electron-deficient ylides. However, their sulfur atom is
more nucleophilic. We hope to convert nucleophilic sulfur
ylides into electrophilic metallocarbenoids through an
umpolung under the catalysis of transition metal catalysts to
initiate the reaction with the nucleophilic thiirane sulfur atom.
Herein, we present an electrophilic ring expansion for the
conversion of strained thiiranes into strained thietanes directly
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was increased to 30 mol% and 40 mol%, the yield decreased
with sulfur ylide-generated metallocarbenoids as electrophiles
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and dimethyl sulfide as a transient nucleophile and leaving
group, resulting in a favorable double nucleophilic substitution
process (Scheme 1). The current method is a new strategy for
the synthesis of functionalized strained thietanes from readily
accessible thiiranes.
slightly (Table 1, entries 10 and 11). Then, we carried out
further optimizations with 10 mol% of pentaerythritol as an
additive at different reaction temperatures and found that when
the temperature was decreased to 70 C or increased to 90 C,
the yield dropped slightly (Table 1, entries 12 and 13).
Furthermore, we screened catalysts and found that
o
o
RESULTS AND DISCCUSION
Rh2(CH3CO2)4,
[Ir(COD)Cl]2
Rh2(C7H15CO2)4,
were also able to give the corresponding
[Rh(COD)Cl]2,
and
17d
At the outset of this study, 2-(phenoxymethyl)thiirane (1a)
2-(dimethyl-4-sulfanylidene)-1-phenylethan-1-one
product 3aa (Table 1, entries 1417). When Rh2(CH3CO2)4 and
Rh2(C7H15CO2)4 were used as the catalysts, the yields of 3aa
were only 47% and 41% with the ratios of cis:trans 1:0.97 and
1:1, respectively (Table 1, entries 14 and 15). Fortunately, using
catalyst [Rh(COD)Cl]2 got 79% NMR yield and 58% isolated
yield of product 3aa (Table 1, entry 16). Comparing with
catalyst [Rh(COD)Cl]2, the catalyst [Ir(COD)Cl]2 only gave
product 3aa in 48% yield with a cis:trans ratio of 1:1 (Table 1,
entry 17). Moreover, the amounts of catalysts Rh2(CF3CO2)4
and Rh2(CH3CO2)4 were reduced to half and it was found that
the catalyst Rh2(CF3CO2)4 had no significant effect on the yield
of product 3aa (Table 1, entry 18). Diazoacetophenone was also
tested instead of 2a as the carbene precursor, no desired product
3aa was observed (Table 1, entries 20 and 21). No product 3aa
was detected when no catalyst was used (Table 1, entry 22) and
similar results were obtained without pentaerythritol as an
additive under the catalysis of [Rh(COD)Cl]2 (Table 1, entry
23). But the yield decreased obviously when the reaction was
conducted without pentaerythritol as an additive under the
catalysis of Rh2(CF3CO2)4 (Table 1, entry 24).
and
9
(sulfonium methylide 2a) were employed as the model
substrates to optimize reaction conditions. We first optimized
the reactant ratio (Table 1, entries 15). When the ratio of 1a:2a
was increased from 1:1 to 1:1.5 to 1:2 (Table 1, entries 1, 3, and
4), the yield increased from 34% to 59% to 76% with similar
ratios of cis:trans from 1:0.89 to 1:0.90. However, when the
ratio of 1a:2a was increased to 1:2.5, the yield was slightly
decreased to 73% (Table 1, entry 5). Solvents were also
screened, when polar solvent MeCN was used, product 3aa was
obtained in 27% yield with a ratio of cis:trans 1:0.62 (Table 1,
entry 6). Product 3aa was obtained in 64% and 68% yields,
respectively, when the weak polar solvents toluene and dioxane
were used (Table 1, entries 7 and 8). We further optimized the
amount of additive pentaerythritol, which was usually used as a
ligand in the carbenoid-participated reactions17f (Table 1,
entries 911). When the amount of pentaerythritol was 10
mol%, the yield was only 57% with a ratio of cis:trans of 1:0.90
(Table 1, entry 9). Next, the amount of additive pentaerythritol
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Table 1. Optimization for the Reaction of 2-(Phenoxymethyl)thiirane (1a) and Sulfonium Ylide 2a[a]
Entry 1a
(mmol)
2a
(mmol)
Solvent
(1 mL)
Yield
(%)b
Catalyst (mol%)
Additive (mol%)
Temp. (oC)
Cis:trans
1
0.125
0.1875
0.125
0.125
0.125
0.125
0.125
0.125
0.125
0.125
0.125
0.125
0.125
0.125
0.125
0.125
0.125
0.1875
0.25
(CF3CO2)4Rh2 (5)
(CF3CO2)4Rh2 (5)
(CF3CO2)4Rh2 (5)
C(CH2OH)4 (20)
C(CH2OH)4 (20)
C(CH2OH)4 (20)
DCE
DCE
DCE
DCE
DCE
MeCN
80
80
80
80
80
80
34
32
59
76
73
27
64
68
57
75
74
62
51
47
1: 0.89
1: 0.89
1: 0.90
1: 0.89
1: 0.92
1: 0.62
1: 1
2
3
4
(CF3CO2)4Rh2 (5) C(CH2OH)4 (20)
5
0.3125
0.25
(CF3CO2)4Rh2 (5)
(CF3CO2)4Rh2 (5)
(CF3CO2)4Rh2 (5)
(CF3CO2)4Rh2 (5)
(CF3CO2)4Rh2 (5)
(CF3CO2)4Rh2 (5)
(CF3CO2)4Rh2 (5)
(CF3CO2)4Rh2 (5)
(CF3CO2)4Rh2 (5)
(CH3CO2)4Rh2 (5)
C(CH2OH)4 (20)
C(CH2OH)4 (20)
C(CH2OH)4 (20)
C(CH2OH)4 (20)
C(CH2OH)4 (10)
C(CH2OH)4 (30)
C(CH2OH)4 (40)
C(CH2OH)4 (20)
C(CH2OH)4 (20)
C(CH2OH)4 (20)
6
7
0.25
Toluene 80
dioxane 80
8
0.25
1: 1
9
0.25
DCE
DCE
DCE
DCE
DCE
DCE
80
80
80
70
90
80
1: 0.89
1: 0.85
1: 0.84
1: 0.86
1: 0.80
1: 0.97
10
11
12
13
14
15
0.25
0.25
0.25
0.25
0.25
(C7H15CO2)4Rh2
(5)
0.25
C(CH2OH)4 (20)
DCE
80
41
1: 1
16
17
0.125
0.25
[Rh(COD)Cl]2 (5) C(CH2OH)4 (20)
[Ir(COD)Cl]2 (5) C(CH2OH)4 (20)
DCE
80
79/58c
1: 0.93
0.125
0.25
DCE
80
48
1: 1
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0.125
0.125
(CF3CO2)4Rh2
(2.5)
0.25
0.25
C(CH2OH)4 (20)
C(CH2OH)4 (20)
DCE
DCE
80
80
74
46
1: 0.84
1: 0.77
1
2
3
[Rh(COD)Cl]2
(2.5)
4
5
6
7
8
9
20
21
22
23
24
0.125
0.125
0.125
0.125
0.125
0.25
0.25
0.25
0.25
0.25
(CF3CO2)4Rh2 (5)
[Ir(COD)Cl]2 (5)
None
C(CH2OH)4 (20)
C(CH2OH)4 (20)
C(CH2OH)4 (20)
None
DCE
DCE
DCE
DCE
DCE
80
80
80
80
80
0d
0d
0
-
-
-
[Rh(COD)Cl]2 (5)
(CF3CO2)4Rh2 (5)
78
52
1: 0.93
1: 0.89
None
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[a] Reactions were conducted on a 0.125 mmol scale of 1a in 1 mL of solvent. [b] NMR yield of the crude product 3aa using 1,3,5-
trimethoxybenzene as an internal standard. [c] Isolated yield. [d] Diazoacetophenone as starting material instead of 2a.
Table 2. Optimization for Additives in the Reaction of 2-(Phenoxymethyl)thiirane (1a) and Sulfonium Ylide 2a[a]
[a] NMR yield of the crude product using 1,3,5-trimethoxybenzene as an internal standard.
To further improve the yield and stereoselectivity of the
product 3aa, different alcohols, including primary, secondary,
tertiary alcohols, diols, triol, and enantiopure hexaol, vicinal
amino alcohols, were tested. However, both yield and
stereoselectivity were not further improved. Ethane-1,2-
diamine was also tried. No reaction occurred (Table 2).
71%. We further extended to more electron-rich 4-
methoxyphenoxymethylthiirane (1d), affording product 3da in
a moderate yield of 62%. However, electron-deficient 2-(4-
chlorophenoxymethyl)thiirane (1e) produced the desired
product 3ea in a low yield of 40%. In comparison with
monosubstituted phenoxymethylthiiranes 1a-e, more electron-
rich dimethyl substituted phenoxymethylthiiranes 1f and 1g
gave rise to the corresponding products 3fa and 3ea in high
yields of 75% and 70%, respectively. For geminal 2,2-
disubstituted
thiiranes,
electron-rich
2-(4-
methylphenoxy)methyl-2-methylthiirane (1h) was converted
into 2,2,4-trisubstituted thietane 3ha in a low yield of 26%. This
is very different from the previous results of the nucleophilic
ring expansion with trimethylsulfoxonium iodide as the ylide
source.15 Furthermore, both benzyloxymethylthiirane (1i) and
Scheme 2. Synthesis of Thietanes from Thiiranes.
(2-phenylethoxymethyl)thiirane
(1j)
generated
the
corresponding products 3ia and 3ja in moderate yields of 57%
and 65%, respectively. We further extended thiiranes 1 from
With the optimized reaction conditions, the reaction scope
was then evaluated (Scheme 2, Table 3). Various thiiranes 1
were subjected to the optimal conditions with sulfonium
benzoylmethylide 2a. The results are presented in Table 3.
Phenoxymethylthiirane (1a) and electron-rich ortho- and meta-
methylphenoxymethylthiiranes (1b-c) gave the corresponding
products 3ba-ca in moderate to good isolated yields of 54% and
phenoxymethylthiiranes
(naphthalen-1-yloxymethyl)thiirane
to
naphthyloxymethylthiiranes,
(1k), (naphthalen-2-
yloxymethyl)thiirane (1l), and (6-bromonaphthalen-2-
yloxymethyl) thiirane (1m), affording the corresponding
products 3ka3ma in moderate yields of 62% to 72%. Aliphatic
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after desulfurization was also observed in GC-MS analysis
2-butylthiirane (1o) also gave rise to the corresponding product
1
2
3
4
5
6
7
3oa in a moderate yield of 59%. For unsubstituted thiirane (1p),
product 3pa was obtained in a very low yield of 9% possibly
due to its high volatility, resulting in a deviation of its amount
involved in the reaction from the added amount.
during monitoring the reaction progress. 2-Arylthiiranes show
different regioselectivity in the electrophilic ring expansion and
2,3-disubstituted thietanes 3’ were obtained as major products
because dimethyl sulfide favorably attacks the more
electrophilic benzylic carbon atom in 2-arylthiiranes after they
nucleophilically attacked the metallocarbenoids generated from
sulfonium ylides and the rhodium catalyst (Scheme 4).
Furthermore, aromatic 2-arylthiiranes 1q1s were attempted.
Relatively low yields were obtained because of their instability.
At the same time, the formation of the corresponding olefins
8
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Table 3. Synthesis of Thietanes 3 from Different Thiiranes 1
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After investigating different substituted thiiranes 1, the scope
of sulfur ylides 2 was studied (Table 4). Generally, (dimethyl-
4-sulfanylidene)-1-arylethan-1-ones 2b and 2c bearing
electron-donating groups worked well to deliver the desired
products 3ab and 3ac in 60% and 80% yields, while (dimethyl-
4-sulfanylidene)-1-arylethan-1-ones 2d2h with electron-
withdrawing groups also worked to give rise to the desired
products 3ad3ah in satisfactory to moderate yields
(40%70%). After replacing the phenyl group with naphthyl,
the corresponding product 3ai was obtained in 34% yield.
Furthermore, a sterically hindered cyclic aliphatic sulfur ylide,
(1-adamantan-1-yl)-2-(dimethyl-l4-sulfanylidene)ethan-1-one
(2j) was prepared and reacted with thiirane 1a to afford the
desired product 3aj in 70% yield. Tert-butyl 2-(dimethyl-4-
sulfanylidene)acetate (2k) was also tried to produce the
corresponding product 3ak in a yield of 40%.
compounds, sulfur ylides had obvious advantages as carbene
precursors. Therefore, besides the studies on the expansion of
thiiranes, the sulfur ylide carbene precursors were also used for
the ring expansion reactions of thietane.
Thietane (4) and sulfur ylide 2a were selected as model
substrates for the reaction optimization (Table 5). The rhodium
catalysts gave the desired products in low yields (Table 5,
entries 13). Fortunately, a moderate yield was obtained under
the catalysis of [Ir(COD)Cl]2 (Table 5, entry 4). CuSO4 was also
attempted as catalyst, but no reaction occurred (Table 5, entry
5). The catalyst [Ir(COD)Cl]2 was finally selected as the
optimal catalyst for the electrophilic ring expansion of thietane.
Table 4. Synthesis of Thietanes 3 from Different Sulfonium
Ylides (Dimethyl-4-sulfanylidene)-1-arylethan-1-ones 2
There had been a few reports on the reactions of diazo
carbonyl compound-generated carbenoids and thietanes for the
synthesis of the five-membered heterocycle thiacyclopentanes
through the ring expansion.20a,20c Compared with diazo carbonyl
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Scheme 3. Attempted Reactions of Substituted Thietanes
and Sulfur Ylide 2a.
Substituted
thietanes,
monosubstituted
2-
phenoxymethylthietane (4a) and disubstituted thietane 3aa
were further explored in the ring expansion. However, only
messy mixture products were obtained (Scheme 3). This is the
reason why further ring expansion product thiacyclopentane
derivatives were not observed in the ring expansion of thiiranes.
Table 5. Optimization for the reaction of thietane (4) and
sulfonium ylide (2a)
Scheme 4. Gram-Scale Reaction.
4
2a
Catalyst
(mmol) (mmol) (5 mol%)
Yield
(%)a
7
Entry
1
2
3
0.125
0.125
0.125
0.25
0.25
0.25
Rh2(CF3CO2)4
Rh2(OAc)4
[Rh(COD)Cl]2 13
10
58
4
0.125
0.25
[Ir(COD)Cl]2
(55)b
5
0.125
0.25
CuSO4
NR
[a] NMR yield of the crude product using 1,3,5-trimethoxybenzene
as an internal standard. [b] Yield of the isolated product.
Under the optimal conditions, thietane (4) was used as an
electrophile to react with different (dimethyl-4-sulfanylidene)-
1-arylethan-1-ones 2. The results are presented in Table 6.
(Dimethyl-4-sulfanylidene)-1-phenylethan-1-one (2a) gave
the desired product 5a in 55% yield. Electron-rich (dimethyl-
4-sulfanylidene)-1-arylethan-1-ones 2b and 2c yielded the
corresponding products 5b and 5c in 66% and 50% yields,
Scheme 5. Further derivations of the synthetic thietane 3tk.
respectively,
while
electron-deficient
(dimethyl-4-
sulfanylidene)-1-arylethan-1-ones 2d and 2e produced the
desired products 5d and 5e in 68% and 74% yields, respectively.
To demonstrate the practical utility of the method, a gram-
scale synthesis of 3aa was performed, and a moderate yield was
realized (Scheme 4). To show further synthetic utility, this
strategy was applied to the synthesis of the thietane derivative
3tk, which could be converted easily into 6 for the synthesis of
thietane nucleosides by referring literature method (Scheme
5).1a,24 Sulfone 7 was obtained in 54% yield by the oxidation of
Table 6. Synthesis of Thiacyclopentanes 5 from Thietane 4
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The above results indicate that dimethyl sulfide plays a
thietane 3tk with H2O2/HCO2H. Only trans-isomeric product
was obtained after silica gel column separation (Scheme 5).25
crucial role in the reaction, first as a nucleophile, and then as a
leaving group, because other carbene precursors
1
2
3
4
5
6
7
8
9
To further understand the reaction mechanism and to extend
the scope of sulfur ylides, 2-(dimethyl(oxo)-6-sulfanylidene)-
1-phenylethan-1-one (8) was prepared and subjected to the ring
expansion. The reaction of 2-butylthiirane (1o) and sulfur ylide
8 afforded the desired product 3oa in 8% yield with a cis and
trans ratio of 1:0.43 accompanied with 2,3-dihydro-1,4-
oxathiines 9 and 10 in 14% yield as byproducts under
conditions A.26 The yield of the desired product 3oa was
slightly increased to 9% when dimethyl sulfide was added as an
additive due to favorable formation of six-membered 2,3-
dihydro-1,4-oxathiines (Scheme 6).
(dimethyl(oxo)-4-sulfanylidene)-1-phenylethan-1-one
(8)
gave the desired product 3aa in a low yield accompanied by 2,3-
dihydro-1,4-oxathiines 9 and 10 as byproducts due to weak
nucleophilicity of dimethyl sulfoxide (Scheme 6).
Diazoacetophenone without dimethyl sulfide does not work
under reaction conditions (Table 1, entries 20 and 21), but
works in the presence of tetrahydrothiophene (Scheme 7). After
obtaining the above information, we proposed the following
reaction mechanism (Scheme 8), first, (dimethyl-4-
sulfanylidene)-1-arylethan-1-ones (sulfur ylides) 2 react with
the metal Rh catalyst to form metallocarbenoid intermediates A
by loss of dimethyl sulfide.17a,17b Then thiiranes 1 as
nucleophiles attack the intermediates A, generating thiirane
sulfonium intermediates B.21b,22b Intermediates B are activated
thiiranium derivatives and can be attacked by dimethyl sulfide
to generate ring-opened intermediates C (and C’) depending on
the substituents of thiiranes.27 In the ring opening reaction, all
2-alkylthiiranes are attacked on their less substituted ring
carbon atom followed by intramolecularly nucleophilic attack
to afford mixtures of cis- and trans-products 3 (Path a).
However, all 2-arylthiiranes are attacked on their more
substituted benzylic ring carbon atom mainly to give rise to
ring-opened intermediates C’ as major intermediates followed
by intramolecularly nucleophilic attack to deliver thietanes 3’
as major products (Path b). The regioselectivity is similar to that
in the Lewis acid AgNO3-catalyzed ring opening reactions of
thiiranes.27
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The reaction of thiirane 1a and diazoacetophenone was
further tested in the presence of sulfide additives. Although no
desired product 3aa was observed in the absence of sulfide
additives, the desired product 3aa was obtained in a trace
amount in the presence of dimethyl sulfide and in 10% yield in
the presence of tetrahydrothiophene. The results reveal that
sulfide can promote the ring expansion (Scheme 7)
To identify the function of dimethyl sulfide: acceleration or
deceleration of the reaction because Me2S may poison the active
catalyst or disfavor the formation of intermediate A, under
optimal conditions, we conducted the model reaction with
additional 2 equiv. of Me2S, giving product 3aa in 79%, the
same as that without additional Me2S. We can conclude that
Me2S does not poison the active catalyst. We also carried out
the model reaction in a round-bottom flask with a reflux
condenser, affording product 3aa in 72% yield, slightly lower
than that in a pressure tube (79% yield, Table 1, entry 16),
indicating the reaction maybe very fast. Before the escape of the
generated Me2S from the reaction mixture, the reaction almost
finished. To verify the assumption, we determined the product
yields at different reaction times for the model reaction. The
profile of yield vs time is shown in Figure 2. The results indicate
that the reaction occurred very fast, almost complete during 15
mins., showing a high turnover number.
Scheme 6. Reaction of 2-Butylthiirane and Sulfoxonium
Benzoylmethylide Ylide 8.
Scheme 7. Reaction of 2-Phenoxymethylthiirane and
Diazoacetophenone.
100
50
0
0
50
100
150
Reaction time (min.)
Scheme 8. Proposed the reaction mechanism.
Figure 2. Profile of Yield vs Time for the Reaction of 1a and
2a.
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effectively utilizes the tension of thiiranes and the
1
2
3
4
5
6
7
8
nucleophilicity of the sulfur atom in thiiranes to react with the
metallocarbenoids generated from safe and relatively easy-to-
prepared carbene precursors, (dimethyl-4-sulfanylidene)-1-
The
reactions
of
(2a)
2-(dimethyl-6-sulfanylidene)-1-
and
2-(dimethyl(oxo)-6-
phenylethan-1-one
sulfanylidene)-1-phenylethan-1-one (8) with 2-butylthiirane
(1o) show different chemoselectivity. The former produced
thietane 3oa as only product (Table 3). However, the later gave
rise to a mixture products of thietane 3oa, 3-butyl-6-phenyl-2,3-
dihydro-1,4-oxathiine (9) and 2-butyl-6-phenyl-2,3-dihydro-
1,4-oxathiine (10) due to poor nucleophilicity of DMSO.
Dimethyl sulfide (DMS) is a good nucleophile, favorably
nucleophilically attacking the less ring carbon atom in the
thiirane in the intermediate Ba to generate intermediate Ca,
which undergoes an intramolecularly nucleophilic cyclization
to afford thietane 3oa (Path a). However, DMSO is a poor
nucleophile, path a is not favorable, the competitive path c
occurs. The intermediate Ba converts into its enolic forms Da
(favorable conformation) and Ea (unfavorable conformation),
which undergo intramolecular ring-opening reactions on their
less and more substituted ring carbon atoms, respectively, to
afford products 9 and 10 (Scheme 9).
arylethan-1-ones
or
tert-butyl
2-(dimethyl-4-
sulfanylidene)acetate. 2-Alkyl and 2-arylthiiranes show
different regioselectivity in their electrophilic ring expansion.
The umpolung from the nucleophilic ylides to the electrophilic
carbenoids plays an important role in both the activation and
ring-opening of less electrophilic thiiranes, even in subsequent
intramolecular substitution because the released dimethyl
sulfide during the umpolung acts as a nucleophile and leaving
group in the subsequent double nucleophilic substitution
process. This strategy provides an efficient route to prepare
functionalized thietanes. Next, more work has to be done to
achieve highly stereochemical control in the preparation of the
expanded products.
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EXPERIMENTAL SECTION
General Information. Unless otherwise noted, all materials
were purchased from commercial suppliers. Flash column
chromatography was performed using silica gel (normal phase,
200-300 mesh) from Branch of Qingdao Haiyang Chemical
Industry. Petroleum ether (PE) used for column
chromatography is 60−90 oC fraction, and the removal of
residue solvent was accomplished under rotovap. Reactions
were monitored by thin-layer chromatography on silica gel
GF254 coated 0.2 mm plates from Institute of Yantai Chemical
Industry. The plates were visualized under UV light, as well as
other TLC stains (10% phosphomolybdic acid in ethanol; 1%
potassium permanganate in water; 10 g of iodine absorbed on
30 g of silica gel). 1H and 13C {1H} NMR spectra were recorded
on a Bruker 400 MHz spectrometer in CDCl3 with TMS as an
internal standard, and the chemical shifts (δ) are reported in
parts per million (ppm). All coupling constants (J) in 1H NMR
spectra are absolute values given in hertz (Hz) with peaks
labeled as singlet (s), broad singlet (brs), doublet (d), triplet (t),
quartet (q), and multiplet (m). The IR spectra (KBr pellets, v
[cm−1]) were taken on a Nicolet 5700 FTIR spectrometer.
HRMS measurements were carried out on an Agilent LC/MSD
TOF mass spectrometer. LRMS measurements were carried out
on Thermo Trace 1300/ISQ QD system. Melting points were
obtained on a Yanaco MP-500 melting point apparatus and are
uncorrected.
Scheme 9. Rationale on the Different Chemoseletivity in the
Reactions of 2-(Dimethyl-6-sulfanylidene)-1-phenylethan-1-
one (2a) and 2-(Dimethyl(oxo)-6-sulfanylidene)-1-
phenylethan-1-one (8) with 2-Butylthiirane (1o).
General Procedure for the Synthesis of Sulfur Ylides 2a-
2j.28
To a solution of 2-bromoacetophenone (1.99 g, 10 mmol) in
acetone (15 mL) was added dimethyl sulfide (620 mg, 10 mmol).
After the mixture had been stirred at room temperature for 12 h,
the residue was filtered and washed with acetone. The solid
product was used as sulfonium bromide without further
purification. The corresponding sulfonium bromide was added
to a solution of NaOH (400 mg, 10 mmol) in water (10 mL).
The solution was stirred at room temperature for 30 min and
then extracted several times with dichloromethane. The
combined organic layers were washed with water and brine
sequentially, dried over Na2SO4, filtered, and concentrated. The
sulfur ylide obtained can be used directly without further
purification. 2a−2i were prepared by the general procedure.
All the results support that dimethyl sulfide serves as a
transient nucleophile and a leaving group in the synthesis of
thietanes from thiiranes through the carbene-induced
electrophilic ring expansion. Dimethyl sulfide participation
changes unfavorable Stevens rearrangement into favorable
double nucleophilic substitution, making the electrophilic ring
expansion smoothly.
CONCLUSIONS
The current reaction presents a new method for the synthesis
of functionalized thietanes from readily available thiiranes
through the electrophilic ring expansion strategy. The strategy
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124.4, 54.8, 28.7. IR (KBr): v = 1510, 1405, 839 cm-1. HRMS
2-(Dimethyl-λ4-sulfanylidene)-1-phenylethan-1-one
(2a).28b Yellow solid 700 mg, 51% yield. M.p.: 37–38 °C, Lit.28c
M.p.: 56–57 °C). 1H NMR (400 MHz, CDCl3) (δ, ppm) = 7.81
– 7.74 (m, 2H, ArH), 7.36 – 7.31 (m, 3H, ArH), 4.33 (br s, 1H),
2.92 (s, 6H). 13C {1H} NMR (101 MHz, CDCl3) (δ, ppm) =
182.6, 140.7, 129.3, 127.6, 126.1, 51.5, 28.3.
2-(Dimethyl-λ4-sulfanylidene)-1-(p-tolyl)ethan-1-one
(2b).28b Yellow solid 533 mg, 55% yield. M.p.: 112–114 °C. 1H
NMR (400 MHz, CDCl3) (δ, ppm) = 7.68 (d, J = 8.3 Hz, 2H,
ArH), 7.14 (d, J = 7.9 Hz, 2H, ArH), 4.30 (s, 1H), 2.99 – 2.98
(m, 6H), 2.35 (s, 3H). 13C {1H} NMR (101 MHz, CDCl3) (δ,
ppm) = 183.2, 139.5, 138.1, 128.5, 126.3, 49.9, 28.5, 21.3.
(ESI-TOF) m/z [M+H]+ calcd for C14H15OS+: 231.0838, found:
1
2
3
4
5
6
7
8
231.0838.
(1-Adamantan-1-yl)-2-(dimethyl-l4-sulfanylidene)ethan-1-
one (2j). White solid 677 mg, 87%. M.p.: 140–142 °C. 1H NMR
(400 MHz, CDCl3) (δ, ppm) = 3.67 (s, 1H), 3.83 – 3.82 (m, 6H),
1.96 (br s, 3H), 1.77 (br s, 3H), 1.70 – 1.64 (m, 6H). 13C {1H}
NMR (101 MHz, CDCl3) (δ, ppm) = 197.7, 48.1, 42.5, 40.1,
37.0, 28.7, 28.7. IR (KBr): v = 2899, 2847, 1483, 850 cm-1.
HRMS (ESI-TOF) m/z [M+H]+ calcd for C14H23OS+: 239.1464,
found: 239.1465.
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Synthesis of Sulfur Ylide 2k.29
2-(Dimethyl-λ4-sulfanylidene)-1-(4-methoxyphenyl)ethan-
1-one (2c).28b Yellow solid 620 mg, 37% yield. M.p.: 106–
108 °C. 1H NMR (400 MHz, CDCl3) (δ, ppm) = 7.74 – 7.71 (m,
2H, ArH), 6.85 – 6.83 (m, 2H, ArH), 4.25 (s, 1H), 3.803 – 3.796
(m, 3H), 2.96 – 2.94 (m, 6H). 13C {1H} NMR (101 MHz, CDCl3)
(δ, ppm) = 182.6, 160.7, 133.5, 127.8, 113.0, 55.2, 50.4, 28.7.
1-(4-Chlorophenyl)-2-(dimethyl-λ4-sulfanylidene)ethan-1-
one (2d).28d White solid 939 mg, 44% yield. M.p.: 119–121 °C.
1H NMR (400 MHz, CDCl3) (δ, ppm) = 7.69 (d, J = 8.5 Hz, 2H,
ArH), 7.28 (d, J = 8.5 Hz, 2H, ArH), 4.26 (s, 1H), 2.97 (s, 6H).
13C {1H} NMR (101 MHz, CDCl3) (δ, ppm) = 181.7, 139.3,
135.3, 127.9, 127.7, 50.9, 28.3.
1-(4-Bromophenyl)-2-(dimethyl-λ4-sulfanylidene)ethan-1-
one (2e).28b Yellow solid 1.27 g, 84% yield. M.p.: 112–113 °C,
Lit.28c M.p: 121–123 °C. 1H NMR (400 MHz, CDCl3) (δ, ppm)
= 7.60 (d, J = 8.4 Hz, 2H, ArH), 7.42 (d, J = 8.5 Hz, 2H, ArH),
4.27 (s, 1H), 2.92 (s, 6H). 13C {1H} NMR (101 MHz, CDCl3)
(δ, ppm) = 181.5, 139.7, 130.8, 127.9, 123.7, 51.5, 28.3.
2-(Dimethyl-λ4-sulfanylidene)-1-(4-nitrophenyl)ethan-1-
one (2f).28b Yellow solid 1.37 g, 94% yield. M.p.: 119–120 °C,
Lit.28c M.p.: 110–111 °C. 1H NMR (400 MHz, CDCl3) (δ, ppm)
= 8.18 – 8.15 (m, 2H, ArH), 7.89 – 7.87 (m, 2H, ArH), 4.42 (s,
1H), 3.02 – 3.01 (s, 6H). 13C {1H} NMR (101 MHz, CDCl3) (δ,
ppm) = 180.1, 148.3, 146.7, 127.2, 123.2, 53.6, 28.0.
A 50 mL round-bottomed flask was charged with tert-butyl
bromoacetate (5.00 g, 25.7 mmol), acetone (15 mL), and
dimethylsulfide (5.1 mL, 69 mmol). The reaction vessel was
sealed and the reaction mixture was stirred at room temperature
overnight, during which the product precipitated. The solid
product was then filtered and washed several times with cold
acetone and dried under reduced pressure to give the product as
a white crystalline solid (6.62 g, 25.7 mmol, quant.). The
product was used in the subsequent step without further
purification or characterization. A 25 mL round-bottomed flask
was
charged
with
(2-(tert-butoxy)-2-
oxoethyl)dimethylsulfonium bromide (1.82 g, 7.10 mmol) and
CHCl3 (8 mL). The reaction mixture was allowed to stir for 5
min until the reaction mixture had become homogeneous. The
reaction mixture was cooled to 0 °C and saturated aq. K2CO3
(4.6 mL) and aq. NaOH solution (1 mL, 12 M, 7.2 mmol) were
added in quick succession with vigorous stirring. The reaction
mixture immediately became heterogeneous and the reaction
mixture was brought to r.t. and stirred. After 15 min the reaction
mixture was filtered, and the top organic layer was separated
from the aqueous layer. The aqueous layer was extracted once
with CHCl3. The combined organics were dried over K2CO3 and
concentrated under reduced pressure to provide the crude
product as an off-white solid in quantitative yield (1.25 g, 7.09
mmol), which was used in the subsequent step without further
purification.
1-(3-Chlorophenyl)-2-(dimethyl-λ4-sulfanylidene)ethan-1-
1
one (2g). Yellow liquid 1.22 g, 65%. H NMR (400 MHz,
tert-Butyl 2-(dimethyl-λ4-sulfanylidene)acetate (2k).29b
CDCl3) (δ, ppm) = 7.74 (t, J = 1.9 Hz, 1H, ArH), 7.61 (dt, J =
7.4, 1.5 Hz, 1H, ArH) 7.30 – 7.22 (m, 2H, ArH), 4.27 (s, 3H),
2.93 (s, 6H). 13C {1H} NMR (101 MHz, CDCl3) (δ, ppm) =
180.9, 142.7, 133.7, 129.1, 129.0, 126.4, 124.3, 52.1, 28.2. IR
(KBr): v = 1574, 1516, 872, 843 cm-1. HRMS (ESI-TOF) m/z
[M+H]+ calcd for C10H12ClOS+: 215.0292, found: 215.0292.
1
White solid quantitative yield (1.25g). M.p.: 61–63 °C. H
NMR (400 MHz, CDCl3) (δ, ppm) = 2.69 (br s, 1H), 2.60 (s,
6H), 1.33 (s, 9H). 13C {1H} NMR (101 MHz, CDCl3) (δ, ppm)
= 170.5, 76.8, 32.9, 30.7, 29.0.
General Procedure for the Synthesis of Sulfur Ylide 8.30
1-(3,4-Dichlorophenyl)-2-(dimethyl-λ4-
In a 125 mL flame-dried round bottom flask attached to a
reflux condenser, under argon atmosphere, potassium tert-
butoxide (3.0 g, 27.2 mmol) and 27.0 mL of anhydrous THF
were added. Then, trimethylsulfoxonium iodide (4.48 g, 20.4
mmol) was added in one portion. After the suspension was
refluxed for 2 hours, the mixture was cooled to 0 °C followed
by slow addition of benzoyl chloride (956 mg, 6.8 mmol). The
reaction temperature was allowed to warm to room temperature
and the mixture was stirred for additional 3 hours. After that, 70
mL of water was added and the product was extracted with a
CH2Cl2:i-PrOH (3:1, v/v) mixture (8×20 mL). The organic
phase was washed with water (3×10 mL), dried over Na2SO4,
and the solvent was removed on a rotary evaporator. The crude
material was purified by recrystallization from a mixture of
petroleum and ethyl acetate.
sulfanylidene)ethan-1-one (2h). Yellowish solid 1.08 g, 58%.
M.p.: 136–138 °C. 1H NMR (400 MHz, CDCl3) (δ, ppm) = 7.85
– 7.84 (m, 1H, ArH), 7.60 – 7.52 (m, 1H, ArH), 7.40 – 7.34 (m,
1H, ArH), 4.26 – 4.25 (m, 1H), 2.97 – 2.96 (m, 6H). 13C {1H}
NMR (101 MHz, CDCl3) (δ, ppm) = 180.0, 140.9, 133.1, 132.0,
129.8, 128.4, 125.5, 51.7, 28.2. IR (KBr): v = 1569, 1515, 1395,
846 cm-1. HRMS (ESI-TOF) m/z [M+H]+ calcd for
C10H11Cl2OS+: 248.9902, found: 248.9902.
2-(Dimethyl-λ4-sulfanylidene)-1-(naphthalen-1-yl)ethan-1-
one (2i). White solid 550 mg, 75%. M.p.: 160–162 °C. 1H NMR
(400 MHz, CDCl3) (δ, ppm) = 8.47 (d, J = 7.9 Hz, 2H, ArH),
7.85 – 7.69 (m, 2H, ArH), 7.48 – 7.37 (m, 3H, ArH), 4.07 (br s,
1H), 3.05 (s, 6H). 13C {1H} NMR (101 MHz, CDCl3) (δ, ppm)
= 175.2, 133.7, 130.6, 128.4, 127.9, 126.3, 125.9, 125.5, 124.9,
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(Dimethyl(oxo)-4-sulfanylidene)-1-phenylethan-1-one
(8). White solid 760 mg, 70% yield. M.p.: 127–128 °C, Lit.30
M.p.: 119–121 °C. R f = 0.33, 5% methol in dichloromethane.
1H NMR (400 MHz, CDCl3) (δ, ppm) = 7.84 – 7.74 (m, 2H,
ArH), 7.48 – 7.34 (m, 3H, ArH), 4.98 (s, 1H), 3.52 – 3.47 (m,
6H). 13C {1H} NMR (101 MHz, CDCl3) (δ, ppm) = 182.3, 138.8,
130.7, 128.1, 126.5, 68.2, 42.4.
126.99, 126.8, 126.7, 120.9, 120.8, 111.5, 111.4, 73.0, 72.7,
1
1
2
3
4
5
6
7
8
37.6, 36.8, 36.7, 35.9, 28.9, 28.2, 16.2, 16.1. Cis-isomer: H
NMR (400 MHz, CDCl3) (δ, ppm) = 7.84 – 7.80 (m, 2H, ArH),
7.60 – 7.55 (m, 1H, ArH), 7.49 – 7.44 (m, 2H, ArH), 7.20 – 7.10
(m, 2H, ArH), 7.92 – 7.79 (m, 2H, ArH), 4.86 – 4.82 (m, 1H),
4.25 (dd, J = 9.5, 6.3 Hz, 1H), 4.12 – 3.96 (m, 2H), 3.44 (ddd,
J = 12.7, 6.3, 6.3 Hz, 1H), 3.12 (ddd, J = 12.9, 8.5, 8.5 Hz, 1H),
2.18 (s, 3H). 13C {1H} NMR (101 MHz, CDCl3) (δ, ppm) =
196.2, 196.1, 156.6, 156.5, 133.9, 133.6, 133.52, 133.47, 130.8,
130.7, 128.8, 128.30, 128.28, 127.05, 126.99, 126.8, 126.7,
120.9, 120.8, 111.5, 111.4, 73.0, 72.7, 37.6, 36.8, 36.7, 35.9,
28.9, 28.2, 16.2, 16.1. IR (KBr): v = 2855, 1682, 1597, 1495,
1382 cm-1. HRMS (ESI-TOF) m/z [M+H]+ calcd for
C18H19O2S+: 299.1100, found: 299.1100.
General Procedure for the Synthesis of Thietanes 3
9
Conditions A:
A pressure tube was charged with
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[Rh(COD)Cl]2 (3 mg, 5 mol %), C(CH2OH)4 (3 mg, 20 mol%),
thiirane (0.125 mmol), sulfoxonium ylide (0.25 mmol), and
DCE (1 mL). The reaction mixture was stirred under N2
conditions at 80 °C in an oil bath for 2 h. After that, the solvent
was removed under reduced pressure and the residue was
purified by silica gel chromatography using PE/EA (10:1, v/v)
as eluent to afford the product 3.
2-(Benzoyl)-4-((3-methylphenyloxy)methyl)thietane (3ca).
Gold yellow solid 26 mg, 71% yield. M.p.: 52–53 °C. Rf = 0.26,
1
10% ethyl acetate in petroleum ether. Trans-isomer: H NMR
(400 MHz, CDCl3) (δ, ppm) = 7.83 – 7.80 (m, 2H, ArH), 7.59 –
7.55 (m, 1H, ArH), 7.48 – 7.44 (m, 2H, ArH), 7.21 – 7.13 (m,
1H, ArH), 6.82 – 6.67 (m, 3H, ArH), 4.82 (dd, J = 8.5, 5.9 Hz,
1H), 4.32 (dd, J = 9.8, 6.4 Hz, 1H), 4.26 – 4.21 (m, 1H), 4.04 –
3.91 (m, 1H), 3.71 (ddd, J = 12.6, 8.8, 5.7 Hz, 1H), 2.83 (ddd,
J = 12.6, 8.5, 5.5 Hz, 1H), 2.35 (s, 3H). 13C {1H} NMR (101
MHz, CDCl3) (δ, ppm) = 196.3, 196.1, 158.5, 158.4, 139.6,
139.5, 133.8, 133.6, 133.5, 133.4, 129.2, 129.1, 128.8, 128.29,
128.28, 122.0, 121.9, 115.6, 115.5, 111.5, 72.9, 72.6, 37.5, 36.8,
Conditions B:
A pressure tube was charged with
(CF3CO2)4Rh2 (4 mg, 5 mol %), C(CH2OH)4 (3 mg, 20 mol%),
thiirane (0.125 mmol), sulfoxonium ylide (0.25 mmol), and
DCE (1 mL). The reaction mixture was stirred under N2
conditions at 80 °C in an oil bath for 2 h. After that, the solvent
was removed under reduced pressure and the residue was
purified by silica gel chromatography using PE/EA (10:1, v/v)
as eluent to afford the product 3.
1
36.4, 35.7, 28.9, 28.3, 21.5, 21.4. Cis-isomer: H NMR (400
2-(Benzoyl)-4-(phenoxymethyl)thietane (3aa). White solid
20 mg, 58% yield. M.p.: 94–97 °C. Rf = 0.24, 10% ethyl acetate
in petroleum ether. Trans-isomer: 1H NMR (400 MHz, CDCl3)
(δ, ppm) = 7.80 – 7.76 (m, 2H, ArH), 7.56 – 7.52 (m, 1H, ArH),
7.45 – 7.41 (m, 2H, ArH), 6.97 – 6.89 (m, 1H, ArH), 6.93 – 6.83
(m, 2H, ArH), 4.81 – 4.77 (m, 1H), 4.30 (dd, J = 9.7, 6.3 Hz,
1H), 4.23 – 4.19 (m, 1H), 4.01 – 3.88 (m, 1H), 3.68 (ddd, J =
MHz, CDCl3) (δ, ppm) = 7.83 – 7.80 (m, 2H, ArH), 7.59 – 7.55
(m, 1H, ArH), 7.48 – 7.44 (m, 2H, ArH), 7.21 – 7.13 (m, 1H,
ArH), 6.82 – 6.67 (m, 3H, ArH), 4.82 (dd, J = 8.5, 5.9 Hz, 1H),
4.26 – 4.21 (m, 1H), 4.09 (dd, J = 9.4, 7.3 Hz, 1H), 4.04 – 3.91
(m, 1H), 3.40 (ddd, J = 12.6, 6.2, 6.2 Hz, 1H), 3.13 (ddd, J =
12.9, 8.7, 8.7 Hz, 1H), 2.32 (s, 3H). 13C {1H} NMR (101 MHz,
CDCl3) (δ, ppm) = 196.3, 196.1, 158.5, 158.4, 139.6, 139.5,
133.8, 133.6, 133.5, 133.4, 129.2, 129.1, 128.8, 128.29, 128.28,
122.0, 121.9, 115.6, 115.5, 111.5, 72.9, 72.6, 37.5, 36.8, 36.4,
35.7, 28.9, 28.3, 21.5, 21.4. IR (KBr): v = 2943, 2861, 1682,
1598, 1583, 1385 cm-1. HRMS (ESI-TOF) m/z [M+H]+ calcd
for C18H19O2S+: 299.1100, found: 299.1100.
12.5, 8.8, 5.7 Hz, 1H), 2.80 (ddd, J = 12.6, 8.5, 5.5 Hz, 1H). 13
C
{1H} NMR (101 MHz, CDCl3) (δ, ppm) = 196.3, 196.1, 158.5,
158.4, 133.9, 133.6, 133.53, 133.47, 129.5, 129.4, 128.8,
128.29, 128.28, 121.2, 121.0, 114.73, 114.66, 72.9, 72.6, 37.5,
1
36.8, 36.4, 35.7, 28.9, 28.3. Cis-isomer: H NMR (400 MHz,
CDCl3) (δ, ppm) = 7.80 – 7.76 (m, 2H, ArH), 7.56 – 7.52 (m,
1H, ArH), 7.45 – 7.41 (m, 2H, ArH), 6.97 – 6.89 (m, 1H, ArH),
6.93 – 6.83 (m, 2H, ArH), 4.81 – 4.77 (m, 1H), 4.23 – 4.19 (m,
1H), 4.07 (dd, J = 9.4, 7.3 Hz, 1H), 4.01 – 3.88 (m, 1H), 3.37
(ddd, J = 12.6, 6.2, 6.2 Hz, 1H), 3.10 (ddd, J = 12.8, 8.7, 8.7
Hz, 1H). 13C {1H} NMR (101 MHz, CDCl3) (δ, ppm) = 196.3,
196.1, 158.5, 158.4, 133.9, 133.6, 133.53, 133.47, 129.5, 129.4,
128.8, 128.29, 128.28, 121.2, 121.0, 114.73, 114.66, 72.9, 72.6,
37.5, 36.8, 36.4, 35.7, 28.9, 28.3. IR (KBr): v = 2942, 2860,
1682, 1598, 1586, 1496, 1387 cm-1. HRMS (ESI-TOF) m/z
[M+H]+ calcd for C17H17O2S+: 285.0944, found: 285.0945.
2-(Benzoyl)-4-((4-methoxyphenoxy)methyl)thietane (3da).
Yellow green solid 24 mg, 62% yield. M.p.: 71–75 °C. Rf = 0.28,
1
10% ethyl acetate in petroleum ether. Trans-isomer: H NMR
(400 MHz, CDCl3) (δ, ppm) = 7.82 – 7.79 (m, 2H, ArH), 7.59 –
7.55 (m, 1H, ArH), 7.48 – 7.44 (m, 2H, ArH), 6.90 – 6.79 (m,
4H, ArH), 4.84 – 4.80 (m, 1H), 4.29 (dd, J = 9.8, 6.3 Hz, 1H),
4.22 – 4.17 (m, 1H), 4.02 – 3.89 (m, 1H), 3.78 (s, 3H), 3.70
(ddd, J = 12.6, 8.8, 5.6 Hz, 1H), 2.82 (ddd, J = 12.6, 8.5, 5.5 Hz,
1H). 13C {1H} NMR (101 MHz, CDCl3) (δ, ppm) = 196.2, 196.0,
157.2, 157.1, 133.8, 133.6, 133.5, 129.4, 129.3, 128.83, 128.82,
128.29, 128.28, 126.1, 125.9, 116.02, 115.95, 73.2, 73.0, 37.4,
2-(Benzoyl)-4-((2-methylphenyloxy)methyl)thietane (3ba).
Gold yellow liquid 20 mg, 57% yield. Rf = 0.26, 10% ethyl
acetate in petroleum ether. Trans-isomer: 1H NMR (400 MHz,
CDCl3) (δ, ppm) = 7.84 – 7.80 (m, 2H, ArH), 7.60 – 7.55 (m,
1H, ArH), 7.49 – 7.44 (m, 2H, ArH), 7.20 – 7.10 (m, 2H, ArH),
7.92 – 7.79 (m, 2H, ArH), 4.86 – 4.82 (m, 1H), 4.34 (dd, J =
9.7, 6.1 Hz, 1H), 4.25 (dd, J = 9.5, 6.3 Hz, 1H), 4.12 – 3.96 (m,
1H), 3.73 (ddd, J = 12.6, 8.8, 5.6 Hz, 1H), 2.86 (ddd, J = 12.5,
8.5, 5.5 Hz, 1H), 2.25 (s, 3H). 13C {1H} NMR (101 MHz,
CDCl3) (δ, ppm) = 196.2, 196.1, 156.6, 156.5, 133.9, 133.6,
133.52, 133.47, 130.8, 130.7, 128.8, 128.30, 128.28, 127.05,
1
36.7, 36.2, 35.5, 28.8, 28.2. Cis-isomer: H NMR (400 MHz,
CDCl3) (δ, ppm) = 7.82 – 7.79 (m, 2H, ArH), 7.59 – 7.55 (m,
1H, ArH), 7.48 – 7.44 (m, 2H, ArH), 6.90 – 6.79 (m, 4H, ArH),
4.84 – 4.80 (m, 1H), 4.22 – 4.17 (m, 1H), 4.05 (dd, J = 9.3, 7.3
Hz, 1H), 4.02 – 3.89 (m, 1H), 3.76 (s, 3H), 3.39 (ddd, J = 12.6,
6.2, 6.2 Hz, 1H), 3.11 (ddd, J = 12.8, 8.6, 8.6 Hz, 1H). 13C {1H}
NMR (101 MHz, CDCl3) (δ, ppm) = 196.2, 196.0, 157.2, 157.1,
133.8, 133.6, 133.5, 129.4, 129.3, 128.83, 128.82, 128.29,
128.28, 126.1, 125.9, 116.02, 115.95, 73.2, 73.0, 37.4, 36.7,
36.2, 35.5, 28.8, 28.2. IR (KBr): v = 2933, 1680, 1596, 1581,
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8.5, 5.5 Hz, 1H), 2.28 – 2.15 (m, 6H). 13C {1H} NMR (101 MHz,
1508, 1384 cm-1. HRMS (ESI-TOF) m/z [M+H]+ C18H19O3S+:
1
2
3
4
5
6
7
8
315.1049, found: 315.1054.
CDCl3) (δ, ppm) = 196.2, 196.1, 154.5, 154.4, 133.9, 133.6,
133.5, 133.4, 131.6, 131.5, 130.2, 130.0, 128.8, 128.29, 128.27,
126.94, 126.89, 126.83, 126.78, 111.7, 111.6, 73.4, 73.1, 37.6,
36.8, 36.7, 35.9, 28.9, 28.3, 20.44, 20.42, 16.1, 16.0. Cis-isomer:
1H NMR (400 MHz, CDCl3) (δ, ppm) = 7.84 – 7.80 (m, 2H,
ArH), 7.59 – 7.55 (m, 1H, ArH), 7.49 – 7.44 (m, 2H, ArH), 7.97
– 7.91 (m, 2H, ArH), 6.70 (d, J = 8.9 Hz, 1H), 4.85 – 4.81 (m,
1H), 4.23 – 4.19 (m, 1H), 4.09 – 3.94 (m, 2H), 3.42 (ddd, J =
12.6, 6.3, 6.3 Hz, 1H), 3.10 (dt, J = 13.0, 8.6, 8.6 Hz, 1H), 2.28
– 2.15 (m, 6H). 13C {1H} NMR (101 MHz, CDCl3) (δ, ppm) =
196.2, 196.1, 154.5, 154.4, 133.9, 133.6, 133.5, 133.4, 131.6,
131.5, 130.2, 130.0, 128.8, 128.29, 128.27, 126.94, 126.89,
126.83, 126.78, 111.7, 111.6, 73.4, 73.1, 37.6, 36.8, 36.7, 35.9,
28.9, 28.3, 20.44, 20.42, 16.1, 16.0. IR (KBr): v = 2920, 1682,
1612, 1581, 1503, 1383, 1302 cm-1. HRMS (ESI-TOF) m/z
[M+H]+ calcd for C19H21O2S+: 313.1257, found: 313.1266.
2-(Benzoyl)-4-((4-chlorophenoxy)methyl)thietane (3ea).
Yellow green liquid 16 mg, 40% yield. Rf = 0.35, 10% ethyl
acetate in petroleum ether. Trans-isomer: 1H NMR (400 MHz,
CDCl3) (δ, ppm) = 7.82 – 7.79 (m, 2H, ArH), 7.59 – 7.55 (m,
1H, ArH), 7.48 – 7.44 (m, 2H, ArH), 7.25 (d, J = 9.0 Hz, 2H),
6.86 (d, J = 9.0 Hz, 2H), 4.83 – 4.79 (m, 1H), 4.29 (dd, J = 9.7,
6.2 Hz, 1H), 4.22 – 4.18 (m, 1H), 4.01 – 3.90 (m, 1H), 3.71 (ddd,
J = 12.6, 8.8, 5.6 Hz, 1H), 2.81 (ddd, J = 12.7, 8.5, 5.5 Hz, 1H).
13C {1H} NMR (101 MHz, CDCl3) (δ, ppm) = 196.2, 196.0,
157.2, 157.1, 133.8, 133.6, 133.5, 129.4, 129.3, 128.83, 128.82,
128.29, 128.28, 126.1, 125.9, 116.02, 115.95, 37.4, 36.7, 36.2,
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
60
1
35.5, 28.8, 28.2. Cis-isomer: H NMR (400 MHz, CDCl3) (δ,
ppm) = 7.82 – 7.79 (m, 2H, ArH), 7.59 – 7.55 (m, 1H, ArH),
7.48 – 7.44 (m, 2H, ArH), 7.21 (d, J = 9.0 Hz, 2H), 6.80 (d, J =
9.0 Hz, 2H), 4.83 – 4.79 (m, 1H), 4.22 – 4.18 (m, 1H), 4.06 (dd,
J = 9.4, 7.3 Hz, 1H), 4.01 – 3.90 (m, 1H), 3.38 (ddd, J = 12.9,
6.1, 6.1 Hz, 1H), 3.13 (ddd, J = 12.9, 8.7, 8.7 Hz, 1H). 13C {1H}
NMR (101 MHz, CDCl3) (δ, ppm) = 196.2, 196.0, 157.2, 157.1,
133.8, 133.6, 133.5, 129.4, 129.3, 128.83, 128.82, 128.29,
128.28, 126.1, 125.9, 116.02, 115.95, 37.4, 36.7, 36.2, 35.5,
28.8, 28.2. IR (KBr): v = 2942, 2858, 1681, 1596, 1581, 1491,
1385 cm-1. HRMS (ESI-TOF) m/z [M+H]+ calcd for
C17H16ClO2S+: 319.0554, found: 319.0548.
2-(Benzoyl)-4-methyl-4-((4-
methylphenoxy)methyl)thietane (3ha). Golden yellow liquid
10 mg, 26% yield. Rf = 0.15, 10% ethyl acetate in petroleum
1
ether. Trans-isomer: H NMR (400 MHz, CDCl3) (δ, ppm) =
7.85 – 7.79 (m, 2H, ArH), 7.59 – 7.53 (m, 1H, ArH), 7.48 – 7.43
(m, 2H, ArH), 7.06 (d, J = 8.6 Hz, 2H), 6.79 (d, J = 8.5 Hz, 2H),
4.80 – 4.76 (m, 1H), 4.24 (d, J = 9.2 Hz, 1H), 4.08 (d, J = 9.3
Hz, 1H), 3.57 (dd, J = 12.8, 5.7 Hz, 1H), 2.75 (dd, J = 12.8, 8.8
Hz, 1H), 2.27 (s, 3H), 1.80 (s, 3H). 13C {1H} NMR (101 MHz,
CDCl3) (δ, ppm) = 196.43, 196.41, 156.9, 156.7, 133.9, 133.5,
133.4, 130.4, 130.1, 129.9, 129.8, 128.8, 128.7, 128.4, 128.3,
114.64, 114.58, 45.81, 45.79, 35.3, 35.2, 34.2, 33.5, 28.5, 28.0,
20.49, 20.46. Cis-isomer: 1H NMR (400 MHz, CDCl3) (δ, ppm)
= 7.85 – 7.79 (m, 2H, ArH), 7.59 – 7.53 (m, 1H, ArH), 7.48 –
7.43 (m, 2H, ArH), 7.12 (d, J = 8.7 Hz, 2H), 6.89 (d, J = 8.5 Hz,
2H), 4.80 – 4.76 (m, 1H), 4.10 (d, J = 9.1 Hz, 1H), 3.98 (d, J =
9.1 Hz, 1H), 3.44 (dd, J = 12.7, 6.9 Hz, 1H), 2.92 (dd, J = 12.6,
8.4 Hz, 1H), 2.31 (s, 3H), 1.61 (s, 3H). 13C {1H} NMR (101
MHz, CDCl3) (δ, ppm) = 196.43, 196.41, 156.9, 156.7, 133.9,
133.5, 133.4, 130.4, 130.1, 129.9, 129.8, 128.8, 128.7, 128.4,
128.3, 114.64, 114.58, 45.81, 45.79, 35.3, 35.2, 34.2, 33.5, 28.5,
28.0, 20.49, 20.46. IR (KBr): v = 2927, 2863, 1685, 1608, 1512,
1384 cm-1. HRMS (ESI-TOF) m/z [M+H]+ calcd for
C19H21O2S+: 313.1257, found: 313.1257.
2-Benzoyl-4-((2,4-dimethylphenoxy)methyl)thietane (3fa).
Orange solid 29 mg, 75% yield. M.p.: 85–89 °C. Rf = 0.43, 10%
ethyl acetate in petroleum ether. Trans-isomer: H NMR (400
1
MHz, CDCl3) (δ, ppm) = 7.86 – 7.76 (m, 2H, ArH), 7.59 – 7.55
(m, 1H, ArH), 7.49 – 7.44 (m, 2H, ArH), 7.09 – 7.01 (m, 1H,
ArH), 6.83 – 6.68 (m, 2H, ArH), 4.86 – 4.81 (m, 1H), 4.32 (dd,
J = 9.7, 6.1 Hz, 1H), 4.26 – 4.19 (m, 1H), 4.13 – 3.95 (m, 1H),
3.72 (ddd, J = 12.6, 8.8, 5.6 Hz, 1H), 2.86 (ddd, J = 12.5, 8.5,
5.6 Hz, 1H), 2.29 (s, 3H), 2.17 (s, 3H). 13C {1H} NMR (101
MHz, CDCl3) (δ, ppm) = 196.2, 196.1, 156.4, 156.2, 138.1,
137.9, 133.9, 133.6, 133.5, 133.4, 128.9, 128.8, 128.5, 128.3,
125.8, 125.7, 125.52, 125.46, 122.8, 122.7, 109.5, 109.4, 73.4,
73.1, 37.6, 36.8, 36.7, 35.9, 28.9, 28.3, 20.05, 20.02, 11.6, 11.5.
Cis-isomer: 1H NMR (400 MHz, CDCl3) (δ, ppm) = 7.86 – 7.76
(m, 2H, ArH), 7.59 – 7.55 (m, 1H, ArH), 7.49 – 7.44 (m, 2H,
ArH), 7.09 – 7.01 (m, 1H, ArH), 6.83 – 6.68 (m, 2H, ArH), 4.86
– 4.81 (m, 1H), 4.26 – 4.19 (m, 1H), 4.13 – 3.95 (m, 2H), 3.43
(ddd, J = 12.3, 6.1, 6.1 Hz, 1H), 3.11 (ddd, J = 13.0, 8.6, 8.6 Hz,
1H), 2.25 (s, 3H), 2.10 (s, 3H). 13C {1H} NMR (101 MHz,
CDCl3) (δ, ppm) = 196.2, 196.1, 156.4, 156.2, 138.1, 137.9,
133.9, 133.6, 133.5, 133.4, 128.9, 128.8, 128.5, 128.3, 125.8,
125.7, 125.52, 125.46, 122.8, 122.7, 109.5, 109.4, 73.4, 73.1,
37.6, 36.8, 36.7, 35.9, 28.9, 28.3, 20.05, 20.02, 11.6, 11.5. IR
(KBr): v = 2940, 2859, 1682, 1597, 1582, 1384 cm-1. HRMS
(ESI-TOF) m/z [M+H]+ calcd for C19H21O2S+: 313.1257, found:
313.1253.
2-(Benzoyl)-4-((benzyloxy)methyl)thietane (3ia). Light
yellow liquid 21 mg, 57% yield. Rf = 0.35, 10% ethyl acetate in
petroleum ether. Trans-isomer: 1H NMR (400 MHz, CDCl3) (δ,
ppm) = 7.82 – 7.79 (m, 2H, ArH), 7.59 – 7.54 (m, 1H, ArH),
7.48 – 7.43 (m, 2H, ArH), 7.37 – 7.27 (m, 5H, ArH), 4.75 (dd,
J = 8.5, 5.5 Hz, 1H), 4.62 (s, 2H), 3.91 – 3.73 (m, 3H), 3.64 –
3.58 (m, 1H), 2.72 (ddd, J = 12.6, 8.5, 5.0 Hz, 1H), 13C {1H}
NMR (101 MHz, CDCl3) (δ, ppm) = 196.4, 196.3, 138.01,
137.98, 133.9, 133.7, 133.5, 133.4, 128.8, 128.44, 128.38,
128.31, 128.28, 127.74, 127.68, 75.8, 75.0, 73.3, 73.2, 37.5,
1
37.1, 36.8, 36.4, 28.9, 28.5. Cis-isomer: H NMR (400 MHz,
2-(Benzoyl)-4-((2,3-dimethylphenoxy)methyl)thietane
(3ga). White solid 27 mg, 70% yield. M.p.: 55–58 °C. Rf = 0.43,
10% ethyl acetate in petroleum ether. Trans-isomer: H NMR
(400 MHz, CDCl3) (δ, ppm) = 7.84 – 7.80 (m, 2H, ArH), 7.59 –
7.55 (m, 1H, ArH), 7.49 – 7.44 (m, 2H, ArH), 7.97 – 7.91 (m,
2H, ArH), 6.76 (d, J = 7.9 Hz, 1H), 4.85 – 4.81 (m, 1H), 4.31
(dd, J = 9.8, 6.1 Hz, 1H), 4.23 – 4.19 (m, 1H), 4.09 – 3.94 (m,
1H), 3.71 (ddd, J = 12.5, 8.8, 5.6 Hz, 1H), 2.85 (ddd, J = 12.5,
CDCl3) (δ, ppm) = 7.82 – 7.79 (m, 2H, ArH), 7.59 – 7.54 (m,
1H, ArH), 7.48 – 7.43 (m, 2H, ArH), 7.37 – 7.27 (m, 5H, ArH),
4.80 (dd, J = 8.5, 6.5 Hz, 1H), 4.53 (s, 2H), 3.91 – 3.73 (m, 2H),
3.64 – 3.58 (m, 1H), 3.30 (ddd, J = 13.0, 6.6, 6.6 Hz, 1H), 3.01
(ddd, J = 12.8, 8.6, 8.6 Hz, 1H). 13C {1H} NMR (101 MHz,
CDCl3) (δ, ppm) = 196.4, 196.3, 138.01, 137.98, 133.9, 133.7,
133.5, 133.4, 128.8, 128.44, 128.38, 128.31, 128.28, 127.74,
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127.68, 75.8, 75.0, 73.3, 73.2, 37.5, 37.1, 36.8, 36.4, 28.9, 28.5.
133.55, 133.49, 129.5, 129.4, 129.15, 129.07, 128.8, 128.31,
IR (KBr): v = 2939, 2863, 1681, 1596, 1581 cm-1. HRMS (ESI-
TOF) m/z [M+H]+ calcd for C18H19O2S+: 299.1100, found:
299.1100.
128.29, 127.7, 127.6, 126.8, 126.7, 126.4, 126.3, 123.8, 123.7,
118.8, 118.7, 107.0, 73.0, 72.7, 37.6, 36.8, 36.4, 35.6, 29.0, 28.3.
Cis-isomer: 1H NMR (400 MHz, CDCl3) (δ, ppm) = 7.83 – 7.09
(m, 12H, ArH), 4.86 – 4.81 (m, 1H), 4.38 – 4.33 (m, 1H), 4.23
(dd, J = 9.6, 7.3 Hz, 1H), 4.19 – 3.98 (m, 1H), 3.46 (ddd, J =
1
2
3
4
5
6
7
8
2-(Benzoyl)-4-((phenethoxy)methyl)thietane
(3ja).
12.6, 6.1, 6.1 Hz, 1H), 3.18 (ddd, J = 12.9, 8.7, 8.7 Hz, 1H). 13
C
Colorless liquid 25 mg, 65% yield. Rf = 0.35, 10% ethyl acetate
in petroleum ether. Trans-isomer: 1H NMR (400 MHz, CDCl3)
(δ, ppm) = 7.81 – 7.77 (m, 2H, ArH), 7.57 – 7.54 (m, 1H, ArH),
7.47 – 7.43 (m, 2H, ArH), 7.31 – 7.17 (m, 5H, ArH), 4.71 (dd,
J = 8.5, 5.6 Hz, 1H), 3.85 – 3.54 (m, 6H), 2.92 (t, J = 7.1 Hz,
2H), 2.66 (ddd, J = 12.2, 8.5, 4.9 Hz, 1H). 13C {1H} NMR (101
MHz, CDCl3) (δ, ppm) = 196.4, 196.2, 138.8, 138.7, 133.9,
133.6, 133.5, 133.4, 128.89, 128.86, 128.8, 128.7, 128.32,
128.28, 126.2, 126.1, 76.3, 75.8, 72.23, 72.19, 37.5, 37.1, 36.8,
36.33, 36.27, 36.1, 28.9, 28.4. Cis-isomer: 1H NMR (400 MHz,
CDCl3) (δ, ppm) = 7.81 – 7.77 (m, 2H, ArH), 7.57 – 7.54 (m,
1H, ArH), 7.47 – 7.43 (m, 2H, ArH), 7.31 – 7.17 (m, 5H, ArH),
4.78 (dd, J = 8.5, 6.5 Hz, 1H), 3.85 – 3.54 (m, 5H), 3.26 (ddd,
J = 12.9, 6.5, 6.5 Hz, 1H), 2.99 (ddd, J = 12.8, 8.6, 8.6 Hz, 1H),
2.86 (t, J = 7.2 Hz, 2H). 13C {1H} NMR (101 MHz, CDCl3) (δ,
ppm) = 196.4, 196.2, 138.8, 138.7, 133.9, 133.6, 133.5, 133.4,
128.89, 128.86, 128.8, 128.7, 128.32, 128.28, 126.2, 126.1,
76.3, 75.8, 72.23, 72.19, 37.5, 37.1, 36.8, 36.33, 36.27, 36.1,
28.9, 28.4. IR (KBr): v = 2857, 1682, 1597, 1581 cm-1. HRMS
(ESI-TOF) m/z [M+H]+ calcd for C19H21O2S+: 313.1257, found:
313.1258.
{1H} NMR (101 MHz, CDCl3) (δ, ppm) = 196.3, 196.1, 156.5,
156.4, 134.4, 133.8, 133.6, 133.55, 133.49, 129.5, 129.4,
129.15, 129.07, 128.8, 128.31, 128.29, 127.7, 127.6, 126.8,
126.7, 126.4, 126.3, 123.8, 123.7, 118.8, 118.7, 107.0, 73.0,
72.7, 37.6, 36.8, 36.4, 35.6, 29.0, 28.3. IR (KBr): v = 2922, 2853,
1681, 1599, 1581, 1510 cm-1. HRMS (ESI-TOF) m/z [M+H]+
calcd for C21H19O2S+: 335.1100, found: 335.1098.
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2-(Benzoyl)-4-(((6-bromonaphthalen-2-yl)oxy)methyl)thi-
eane (3ma). White solid 32 mg, 62% yield. M.p.: 109–115 °C.
Rf = 0.33, 10% ethyl acetate in petroleum ether. Trans-isomer:
1H NMR (400 MHz, CDCl3) (δ, ppm) = 7.92 – 7.09 (m, 11H,
ArH), 4.85 – 4.81 (m, 1H), 4.43 (dd, J = 9.7, 6.3 Hz, 1H), 4.36
– 4.32 (m, 1H), 4.09 – 3.98 (m, 1H), 3.75 (ddd, J = 12.5, 8.8,
5.6 Hz, 1H), 2.87 (ddd, J = 13.3, 8.5, 5.5 Hz, 1H). 13C {1H}
NMR (101 MHz, CDCl3) (δ, ppm) = 196.2, 196.0, 156.8, 156.6,
133.8, 133.6, 133.52, 133.50, 132.9, 130.2, 130.1, 129.7,
129.64, 129.59, 129.57, 128.82, 128.80, 128.6, 128.5, 128.39,
128.36, 128.28, 128.26, 119.81, 119.75, 117.3, 117.2, 106.98,
106.96, 72.9, 72.7, 37.5, 36.7, 36.3, 35.6, 28.9, 28.2. Cis-isomer:
1H NMR (400 MHz, CDCl3) (δ, ppm) = 7.92 – 7.09 (m, 11H,
ArH), 4.85 – 4.81 (m, 1H), 4.36 – 4.32 (m, 1H), 4.21 (dd, J =
9.5, 7.3 Hz, 1H), 4.09 – 3.98 (m, 1H), 3.45 (ddd, J = 12.4, 6.0,
6.0 Hz, 1H), 3.18 (ddd, J = 13.0, 8.8, 8.8 Hz, 1H). 13C {1H}
NMR (101 MHz, CDCl3) (δ, ppm) = 196.2, 196.0, 156.8, 156.6,
133.8, 133.6, 133.52, 133.50, 132.9, 130.2, 130.1, 129.7,
129.64, 129.59, 129.57, 128.82, 128.80, 128.6, 128.5, 128.39,
128.36, 128.28, 128.26, 119.81, 119.75, 117.3, 117.2, 106.98,
106.96, 72.9, 72.7, 37.5, 36.7, 36.3, 35.6, 28.9, 28.2. IR (KBr):
v = 2942, 1680, 1590, 1500, 1389 cm-1. HRMS (ESI-TOF) m/z
[M+H]+ calcd for C21H18BrO2S+: 413.0205, found: 413.0203.
2-Benzoyl-4-((naphthalen-1-yloxy)methyl)thietane (3ka).
Golden yellow liquid 30 mg, 72% yield. Rf = 0.39, 10% ethyl
acetate in petroleum ether. Trans-isomer: 1H NMR (400 MHz,
CDCl3) (δ, ppm) = 8.29 – 8.25 (m, 1H, ArH), 7.85 – 7.34 (m,
10H, ArH), 6.87 (d, J = 7.4 Hz, 1H, ArH), 4.90 – 4.84 (m, 1H),
4.51 (dd, J = 9.6, 6.2 Hz, 1H), 4.46 – 4.39 (m, 1H), 4.24 – 4.09
(m, 1H), 3.79 (ddd, J = 12.6, 8.8, 5.5 Hz, 1H), 2.95 (ddd, J =
12.6, 8.5, 5.7 Hz, 1H). 13C {1H} NMR (101 MHz, CDCl3) (δ,
ppm) = 196.2, 196.1, 154.2, 154.1, 134.5, 134.4, 133.8, 133.6,
133.55, 133.50, 128.8, 128.3, 127.5, 127.4, 126.5, 126.4,
125.73, 125.71, 125.6, 125.5, 125.3, 125.2, 121.90, 121.86,
120.8, 120.6, 105.12, 105.10, 73.0, 72.8, 37.6, 36.8, 36.6, 35.7,
29.0, 28.3. Cis-isomer: 1H NMR (400 MHz, CDCl3) (δ, ppm) =
8.22 – 8.18 (m, 1H, ArH), 7.85 – 7.34 (m, 10H, ArH), 6.81 (d,
J = 7.4 Hz, 1H), 4.90 – 4.84 (m, 1H), 4.46 – 4.39 (m, 1H), 4.29
(dd, J = 9.5, 7.3 Hz, 1H), 3.52 (ddd, J = 12.7, 6.3, 6.3 Hz, 1H),
3.19 (ddd, J = 12.9, 8.7, 8.7 Hz, 1H). 13C {1H} NMR (101 MHz,
CDCl3) (δ, ppm) = 196.2, 196.1, 154.2, 154.1, 134.5, 134.4,
133.8, 133.6, 133.55, 133.50, 128.8, 128.3, 127.5, 127.4, 126.5,
126.4, 125.73, 125.71, 125.6, 125.5, 125.3, 125.2, 121.90,
121.86, 120.8, 120.6, 105.12, 105.10, 73.0, 72.8, 37.6, 36.8,
36.6, 35.7, 29.0, 28.3. IR (KBr): v = 3062, 2868, 1689, 1581,
1509 cm-1. HRMS (ESI-TOF) m/z [M+H]+ calcd for
C21H19O2S+: 335.1100, found: 335.1100.
(4-Benzylthietan-2-yl)(phenyl)methanone (3na). Colorless
liquid 10 mg, 38% yield. Rf = 0.63, 10% ethyl acetate in
petroleum ether. Trans-isomer: 1H NMR (400 MHz, CDCl3) (δ,
ppm) = 7.80 – 7.77 (m, 2H, ArH), 7.59 – 7.51 (m, 1H, ArH),
7.48 – 7.40 (m, 2H, ArH), 7.30 – 7.15 (m, 5H, ArH), 4.62 (dd,
J = 8.6, 4.3 Hz, 1H), 4.03 – 3.90 (m, 1H), 3.56 (ddd, J = 12.4,
8.3, 4.3 Hz, 1H), 3.19 (dd, J = 13.8, 6.4 Hz, 1H), 3.14 – 3.04
(m, 1H), 2.80 (ddd, J = 12.3, 8.6, 7.0 Hz, 1H). 13C {1H} NMR
(101 MHz, CDCl3) (δ, ppm) = 196.6, 196.2, 138.2, 138.0, 134.1,
133.8, 133.5, 133.3, 128.8, 128.7, 128.62, 128.61, 128.5, 128.4,
128.3, 126.7, 126.6, 45.2, 45.1, 40.8, 39.6, 36.3, 32.2, 31.7. Cis-
isomer: 1H NMR (400 MHz, CDCl3) (δ, ppm) = 7.86 – 7.81 (m,
2H, ArH), 7.59 – 7.51 (m, 1H, ArH), 7.48 – 7.40 (m, 2H, ArH),
7.30 – 7.15 (m, 5H, ArH), 4.77 (dd, J = 8.1, 7.2 Hz, 1H), 4.03
– 3.90 (m, 1H), 3.36 (ddd, J = 12.5, 7.3, 7.3 Hz, 1H), 3.14 –
3.04 (m, 1H), 3.02 – 2.92 (m, 2H). 13C {1H} NMR (101 MHz,
CDCl3) (δ, ppm) = 196.6, 196.2, 138.2, 138.0, 134.1, 133.8,
133.5, 133.3, 128.8, 128.7, 128.62, 128.61, 128.5, 128.4, 128.3,
126.7, 126.6, 45.2, 45.1, 40.8, 39.6, 36.3, 32.2, 31.7. IR (KBr):
v = 2922, 2849, 1716, 1681, 1635, 1449, 1169 cm-1. HRMS
(ESI-TOF) m/z [M+H]+ calcd for C17H17OS+: 269.0995, found:
269.0995.
2-(Benzoyl)-4-((naphthalen-2-yloxy)methyl)thietane (3la).
Light green liquid 27 mg, 65% yield. Rf = 0.38, 10% ethyl
acetate in petroleum ether. Trans-isomer: 1H NMR (400 MHz,
CDCl3) (δ, ppm) = 7.83 – 7.09 (m, 12H, ArH), 4.86 – 4.81 (m,
1H), 4.44 (dd, J = 9.7, 6.3 Hz, 1H), 4.38 – 4.33 (m, 1H), 4.19 –
3.98 (m, 1H), 3.75 (ddd, J = 12.6, 8.8, 5.7 Hz, 1H), 2.87 (ddd,
J = 12.6, 8.5, 5.5 Hz, 1H). 13C {1H} NMR (101 MHz, CDCl3)
(δ, ppm) = 196.3, 196.1, 156.5, 156.4, 134.4, 133.8, 133.6,
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The Journal of Organic Chemistry
2-(Benzoyl)-4-(butyl)thietane (3oa). Yellow green liquid 17
1H), 3.55 (dd, J = 8.6, 8.6 Hz, 1H), 3.30 (dd, J = 8.9, 8.9 Hz,
1H), 2.26 (s, 3H). 13C {1H} NMR (101 MHz, CDCl3) (δ, ppm)
= 195.8, 139.9, 137.0, 133.9, 133.6, 129.4, 128.8, 128.4, 126.4,
48.4, 43.4, 29.2, 21.1. 2-(Benzoyl)-4-(4-methylphenyl)thietane
(3ra) 1H NMR (400 MHz, CDCl3) (δ, ppm) = 7.79 – 7.09 (m,
9H, ArH), 4.87 (dd, J = 8.4, 8.4 Hz, 1H), 4.62 (dd, J = 8.6, 3.5
Hz, 1H), 3.72 (ddd, J = 12.1, 8.4, 3.6 Hz, 1H), 3.14 (ddd, J =
12.3, 8.4, 8.4 Hz, 1H), 2.29 (s, 3H). 13C {1H} NMR (101 MHz,
CDCl3) (δ, ppm) = 195.8, 139.9, 137.0, 133.9, 133.6, 129.4,
128.8, 128.4, 126.4, 48.4, 43.4, 29.2, 21.1. IR (KBr): v = 2920,
2850, 1681, 1597, 1581, 1514, 1384 cm-1. HRMS (ESI-TOF)
m/z [M+H]+ calcd for C17H17OS+: 269.0995, found: 269.0995.
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2
3
4
5
6
7
8
mg, 59% yield. Rf = 0.40, 10% ethyl acetate in petroleum ether.
Trans-isomer: H NMR (400 MHz, CDCl3) (δ, ppm) = 7.76 –
1
7.72 (m, 2H, ArH), 7.50 – 7.46 (m, 1H, ArH), 7.39 – 7.35 (m,
2H, ArH), 4.57 (dd, J = 8.6, 4.3 Hz, 1H), 3.67 – 3.61 (m, 1H),
3.49 (ddd, J = 12.5, 8.3, 4.4 Hz, 1H), 2.63 – 2.53 (m, 1H), 1.85
– 0.78 (m, 9H). 13C {1H} NMR (101 MHz, CDCl3) (δ, ppm) =
196.6, 196.4, 134.1, 133.8, 133.4, 133.2, 128.71, 128.68,
128.34, 128.26, 40.4, 39.15, 39.07, 38.9, 36.7, 36.6, 32.7, 32.3,
1
28.7, 28.4, 22.3, 22.2, 14.0. Cis-isomer: H NMR (400 MHz,
9
CDCl3) (δ, ppm) = 7.76 – 7.72 (m, 2H, ArH), 7.50 – 7.46 (m,
1H, ArH), 7.39 – 7.35 (m, 2H, ArH), 4.72 (dd, J = 7.7, 7.7 Hz,
1H), 3.67 – 3.61 (m, 1H), 3.16 (ddd, J = 12.3, 7.5, 7.5 Hz, 1H),
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2.90 (ddd, J = 12.3, 8.2, 8.2 Hz, 1H), 1.85 – 0.78 (m, 9H). 13
C
2-(Benzoyl)-3-(4-chlorophenyl)thietane (3’sa) and 2-
(Benzoyl)-4-(4-chlorophenyl)thietane (3sa). Colorless liquid
12 mg, 38% yield. Rf = 0.62, 10% ethyl acetate in petroleum
ether. 2-(Benzoyl)-3-(4-chlorophenyl)thietane (3’sa). 1H NMR
(400 MHz, CDCl3) (δ, ppm) = 7.86 – 7.77 (m, 2H, ArH), 7.60 –
7.54 (m, 1H, ArH), 7.47 – 7.43 (m, 2H, ArH), 7.37 – 7.30 (m,
4H, ArH), 5.05 (ddd, J = 8.6, 8.6, 8.6 Hz, 1H), 4.94 (d, J = 7.9
Hz, 1H), 3.60 (dd, J = 8.7, 8.7 Hz, 1H), 3.38 (dd, J = 9.0, 9.0
Hz, 1H). 13C {1H} NMR (101 MHz, CDCl3) (δ, ppm) = 196.1,
195.5, 141.4, 141.2, 133.7, 133.6, 133.4, 133.0, 128.82, 128.80,
128.76, 128.71, 128.68, 128.30, 128.26, 127.9, 48.1, 43.0, 41.5,
35.5, 35.3, 28.9. 2-(Benzoyl)-4-(4-methylphenyl)thietane (3sa).
1H NMR (400 MHz, CDCl3) (δ, ppm) = 7.86 – 7.30 (m, 9H,
ArH), 4.91 (dd, J = 8.2, 8.2 Hz, 1H), 4.69 (dd, J = 8.7, 3.6 Hz,
1H), 3.81 (ddd, J = 12.4, 8.5, 3.7 Hz, 1H), 3.16 (ddd, J = 12.4,
8.3, 8.3 Hz, 1H). 13C {1H} NMR (101 MHz, CDCl3) (δ, ppm) =
196.1, 195.5, 141.4, 141.2, 133.7, 133.6, 133.4, 133.0, 128.82,
128.80, 128.76, 128.71, 128.68, 128.30, 128.26, 127.9, 48.1,
43.0, 41.5, 35.5, 35.3, 28.9. IR (KBr): v = 2930, 2889, 1686,
1600, 1495 cm-1. HRMS (ESI-TOF) m/z [M+H]+ calcd for
C16H14ClOS+: 289.0448, found: 289.0447.
{1H} NMR (101 MHz, CDCl3) (δ, ppm) = 196.6, 196.4, 134.1,
133.8, 133.4, 133.2, 128.71, 128.68, 128.34, 128.26, 40.4,
39.15, 39.07, 38.9, 36.7, 36.6, 32.7, 32.3, 28.7, 28.4, 22.3, 22.2,
14.0. IR (KBr): v = 2956, 2929, 2857, 1682, 1597, 1581 cm-1.
HRMS (ESI-TOF) m/z [M+H]+ calcd for C14H19OS+: 235.1151,
found: 235.1151.
2-Benzoylthietane (3pa). Colorless liquid 2 mg, 9% yield. Rf
1
= 0.44, 10% ethyl acetate in petroleum ether. H NMR (400
MHz, CDCl3) (δ, ppm) = 7.81 – 7.79 (m, 2H, ArH), 7.60 – 7.53
(m, 1H, ArH), 7.47 – 7.44 (m, 2H, ArH), 4.85 (dd, J = 8.3, 6.0
Hz, 1H), 3.57 (dddd, J = 12.4, 9.5, 6.3, 6.3 Hz, 1H), 3.29 (ddd,
J = 9.3, 8.7, 6.5 Hz, 1H), 3.20 (ddd, J = 9.4, 8.7, 5.8 Hz, 1H),
3.02 (dddd, J = 12.2, 9.3, 8.3, 5.8 Hz, 1H). 13C {1H} NMR (101
MHz, CDCl3) (δ, ppm) = 197.6, 133.7, 129.1, 128.6, 40.7, 26.7,
23.0. IR (KBr): v = 2927, 2860, 1686, 1615 cm-1. HRMS (ESI-
TOF) m/z [M+H]+ calcd for C10H11OS+: 179.0525, found:
179.0525.
2-(Benzoyl)-3-(phenyl)thietane (3’qa) and 2-(Benzoyl)-4-
(phenyl)thietane (3qa). Colorless liquid 12 mg, 38% yield. Rf =
0.62, 10% ethyl acetate in petroleum ether. 2-(Benzoyl)-3-
(phenyl)thietane (3’qa). 1H NMR (400 MHz, CDCl3) (δ, ppm)
= 7.77 – 7.74 (m, 2H, ArH), 7.50 – 7.46 (m, 1H, ArH), 7.43 –
7.17 (m, 7H, ArH), 5.02 (ddd, J = 8.5, 8.5, 8.5 Hz, 1H), 4.94 (d,
J = 7.8 Hz, 1H), 3.58 (dd, J = 8.7, 8.7 Hz, 1H), 3.32 (dd, J = 9.0,
9.0 Hz, 1H). 13C {1H} NMR (101 MHz, CDCl3) (δ, ppm) =
195.7, 142.8, 133.9, 133.6, 128.81, 128.78, 128.6, 128.4, 127.7,
127.3, 126.5, 48.2, 43.6, 29.1. 2-(Benzoyl)-4-(phenyl)thietane
(3qa). 1H NMR (400 MHz, CDCl3) (δ, ppm) = 7.77 – 7.74 (m,
2H, ArH), 7.50 – 7.46 (m, 1H, ArH), 7.43 – 7.17 (m, 7H, ArH),
4.90 (dd, J = 8.3, 8.3 Hz, 1H), 4.63 (dd, J = 8.6, 3.5 Hz, 1H),
3.75 (ddd, J = 12.2, 8.5, 3.6 Hz, 1H), 3.15 (ddd, J = 12.3, 8.4,
8.4 Hz, 1H). 13C {1H} NMR (101 MHz, CDCl3) (δ, ppm) =
195.7, 142.8, 133.9, 133.6, 128.81, 128.78, 128.6, 128.4, 127.7,
127.3, 126.5, 48.2, 43.6, 29.1. IR (KBr): v = 2925, 2855, 1681,
1598, 1582, 1493 cm-1. HRMS (ESI-TOF) m/z [M+H]+ calcd
for C16H15OS+: 255.0838, found: 255.0838.
2-(4-Methylbenzoyl)-4-(phenoxymethyl)thietane
(3ab).
Green solid 25 mg, 68% yield. M.p.: 112–114 °C. Rf = 0.40, 10%
1
ethyl acetate in petroleum ether. Trans-isomer: H NMR (400
MHz, CDCl3) (δ, ppm) = 7.65 – 6.78 (m, 9H, ArH), 4.74 – 4.70
(m, 1H), 4.25 (dd, J = 9.7, 6.4 Hz, 1H), 4.18 – 4.13 (m, 1H),
3.95 – 3.82 (m, 1H), 3.63 (ddd, J = 12.6, 8.8, 5.7 Hz, 1H), 2.73
(ddd, J = 12.6, 8.5, 5.4 Hz, 1H), 2.32 – 3.32 (m, 3H). 13C {1H}
NMR (101 MHz, CDCl3) (δ, ppm) = 196.0, 195.8, 158.5, 158.4,
144.43, 144.37, 131.3, 131.1, 129.5, 129.4, 128.4, 121.2, 121.0,
114.72, 114.66, 73.0, 72.6, 37.5, 36.7, 36.3, 35.6, 28.9, 28.3,
21.7. Cis-isomer: 1H NMR (400 MHz, CDCl3) (δ, ppm) = 7.65
– 6.78 (m, 9H, ArH), 4.74 – 4.70 (m, 1H), 4.18 – 4.13 (m, 1H),
4.18 – 4.13 (m, 1H), 4.02 (dd, J = 9.4, 7.3 Hz, 1H), 3.95 – 3.82
(m, 1H), 3.31 (ddd, J = 12.6, 6.2, 6.2 Hz, 1H), 3.03 (ddd, J =
12.8, 8.6, 8.6 Hz, 1H), 2.32 – 3.32 (m, 3H). 13C {1H} NMR (101
MHz, CDCl3) (δ, ppm) = 196.0, 195.8, 158.5, 158.4, 144.43,
144.37, 131.3, 131.1, 129.5, 129.4, 128.4, 121.2, 121.0, 114.72,
114.66, 73.0, 72.6, 37.5, 36.7, 36.3, 35.6, 28.9, 28.3, 21.7. IR
(KBr): v = 2935, 1678, 1600, 1586, 1496, 1384 cm-1. HRMS
(ESI-TOF) m/z [M+H]+ calcd for C18H19O2S+: 299.1100, found:
299.1105.
2-(Benzoyl)-3-(4-methylphenyl)thietane (3’ra) and 2-
(Benzoyl)-4-(4-methylphenyl)thietane (3ra). Yellow solid 11
mg, 34% yield. M.p.: 95–98 °C. Rf = 0.68, 10% ethyl acetate in
petroleum ether. 2-(Benzoyl)-3-(4-methylphenyl)thietane
(3’ra) 1H NMR (400 MHz, CDCl3) (δ, ppm) = 7.77 – 7.74 (m,
2H, ArH), 7.50 – 7.46 (m, 1H, ArH), 7.36 (t, J = 7.7 Hz, 2H,
ArH), 7.24 (d, J = 8.0 Hz, 2H, ArH), 7.10 (d, J = 8.0 Hz, 2H,
ArH), 4.96 (ddd, J = 8.4, 8.4, 8.4 Hz, 1H), 4.91 (d, J = 7.9 Hz,
2-(4-Methoxybenzoyl)-4-(phenoxymethyl)thietane (3ac).
Yellow white solid 31 mg, 80% yield. M.p.: 154–157 °C. Rf =
1
0.23, 10% ethyl acetate in petroleum ether. Trans-isomer: H
NMR (400 MHz, CDCl3) (δ, ppm) = 7.78 – 7.75 (m, 2H, ArH),
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7.34 – 7.15 (m, 2H, ArH), 7.05 – 6.82 (m, 5H, ArH), 4.79 – 4.74
72.8, 72.5, 37.4, 36.6, 36.5, 35.8, 28.9, 28.2. IR (KBr): v = 2931,
2873, 1683, 1592, 1501 cm-1. HRMS (ESI-TOF) m/z [M+H]+
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3
4
5
6
7
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(m, 1H), 4.31 (dd, J = 9.7, 6.4 Hz, 1H), 4.24 – 4.19 (m, 1H),
4.02 – 3.87 (m, 1H), 3.84 – 3.83 (m, 3H), 3.69 (ddd, J = 12.6,
8.9, 5.8 Hz, 1H), 2.77 (ddd, J = 12.6, 8.5, 5.3 Hz, 1H). 13C {1H}
NMR (101 MHz, CDCl3) (δ, ppm) = 195. 0, 194.9, 163.8, 163.7,
158.6, 158.4, 130.6, 129.5, 129.4, 126.8, 126.6, 121.2, 121.0,
114.73, 114.66, 114.0, 73.0, 72.7, 55.5, 37.4, 36.5, 36.4, 35.7,
28.9, 28.4. Cis-isomer: 1H NMR (400 MHz, CDCl3) (δ, ppm) =
7.78 – 7.75 (m, 2H, ArH), 7.34 – 7.15 (m, 2H, ArH), 7.05 – 6.82
(m, 5H, ArH), 4.79 – 4.74 (m, 1H), 4.24 – 4.19 (m, 1H), 4.08
(dd, J = 9.4, 7.3 Hz, 1H), 4.02 – 3.87 (m, 1H), 3.84 – 3.83 (m,
3H), 3.37 (ddd, J = 12.7, 6.3, 6.3 Hz, 1H), 3.07 (ddd, J = 12.8,
8.6, 8.6 Hz, 1H). 13C {1H} NMR (101 MHz, CDCl3) (δ, ppm) =
195. 0, 194.9, 163.8, 163.7, 158.6, 158.4, 130.6, 129.5, 129.4,
126.8, 126.6, 121.2, 121.0, 114.73, 114.66, 114.0, 73.0, 72.7,
55.5, 37.4, 36.5, 36.4, 35.7, 28.9, 28.4. IR (KBr): v = 2930, 2869,
1676, 1602, 1512, 1378 cm-1. HRMS (ESI-TOF) m/z [M+H]+
calcd for C18H19O3S+: 315.1049, found: 315.1050.
calcd for C17H16BrO2S+: 363.0049, found: 363.0051.
2-(4-Nitrobenzoyl)-4-(phenoxymethyl)thietane (3af). White
solid 22 mg, 54% yield. M.p.: 130–136 °C. Rf = 0.16, 10% ethyl
acetate in petroleum ether. Trans-isomer: 1H NMR (400 MHz,
CDCl3) (δ, ppm) = 8.32 – 8.29 (m, 2H, ArH), 7.97 – 7.94 (m,
2H, ArH), 7.33 – 7.25 (m, 2H, ArH), 7.01 – 6.87 (m, 3H, ArH),
4.82 – 4.77 (m, 1H), 4.32 (dd, J = 9.8, 6.0 Hz, 1H), 4.26 – 4.21
(m, 1H), 4.07 – 3.97 (m, 1H), 3.70 (ddd, J = 12.6, 8.7, 5.2 Hz,
1H), 2.91 (ddd, J = 12.6, 8.4, 5.9 Hz, 1H). 13C {1H} NMR (101
MHz, CDCl3) (δ, ppm) = 195.3, 195.1, 158.5, 158.4, 132.6,
132.4, 132.2, 132.1, 129.8, 129.5, 129.4, 128.8, 128.7, 121.3,
121.1, 114.8, 114.7, 72.8, 72.6, 37.4, 36.6, 36.5, 35.8, 28.9, 28.2.
Cis-isomer: 1H NMR (400 MHz, CDCl3) (δ, ppm) = 8.32 – 8.29
(m, 2H, ArH), 7.97 – 7.94 (m, 2H, ArH), 7.33 – 7.25 (m, 2H,
ArH), 7.01 – 6.87 (m, 3H, ArH), 4.82 – 4.77 (m, 1H), 4.26 –
4.21 (m, 1H), 4.10 (dd, J = 9.3, 7.2 Hz, 1H), 4.07 – 3.97 (m,
1H), 3.42 (ddd, J = 12.9, 5.9, 5.9 Hz, 1H), 3.19 (ddd, J = 12.9,
8.6, 8.6 Hz, 1H). 13C {1H} NMR (101 MHz, CDCl3) (δ, ppm) =
195.3, 195.1, 158.5, 158.4, 132.6, 132.4, 132.2, 132.1, 129.8,
129.5, 129.4, 128.8, 128.7, 121.3, 121.1, 114.8, 114.7, 72.8,
72.6, 37.4, 36.6, 36.5, 35.8, 28.9, 28.2. IR (KBr): v = 2953, 2867,
1692, 1602, 1529, 1517, 1347 cm-1. HRMS (ESI-TOF) m/z
[M+H]+ calcd for C17H16NO4S+: 330.0795, found: 330.0805.
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2-(4-Chlorobenzoyl)-4-(phenoxymethyl)thietane
(3ad).
Yellow white solid 28 mg, 70% yield. M.p.: 121–125 °C. Rf =
1
0.37, 10% ethyl acetate in petroleum ether. Trans-isomer: H
NMR (400 MHz, CDCl3) (δ, ppm) = 7.79 – 7.71 (m, 2H, ArH),
7.45 – 7.42 (m, 2H, ArH), 7.34 – 7.24 (m, 2H, ArH), 7.03 – 6.84
(m, 3H, ArH), 4.80 – 4.72 (m, 1H), 4.32 (dd, J = 9.8, 6.2 Hz,
1H), 4.26 – 4.21 (m, 1H), 4.06 – 3.90 (m, 1H), 3.70 (ddd, J =
12.6, 8.8, 5.6 Hz, 1H), 2.84 (ddd, J = 12.6, 8.5, 5.6 Hz, 1H). 13
C
{1H} NMR (101 MHz, CDCl3) (δ, ppm) = 195.1, 194.9, 158.5,
158.4, 140.0, 139.9, 132.2, 131.9, 129.7, 129.5, 129.4, 129.2,
121.3, 121.1, 114.73, 114.66, 72.8, 72.5, 37.4, 36.6, 36.5, 35.8,
28.8, 28.2. Cis-isomer: 1H NMR (400 MHz, CDCl3) (δ, ppm) =
7.79 – 7.71 (m, 2H, ArH), 7.45 – 7.42 (m, 2H, ArH), 7.34 – 7.24
(m, 2H, ArH), 7.03 – 6.84 (m, 3H, ArH), 4.80 – 4.72 (m, 1H),
4.26 – 4.21 (m, 1H), 4.09 (dd, J = 9.4, 7.3 Hz, 1H), 4.06 – 3.90
(m, 1H), 3.40 (ddd, J = 12.6, 6.2, 6.2 Hz, 1H), 3.13 (ddd, J =
12.9, 8.6, 8.6 Hz, 1H). 13C {1H} NMR (101 MHz, CDCl3) (δ,
ppm) = 195.1, 194.9, 158.5, 158.4, 140.0, 139.9, 132.2, 131.9,
129.7, 129.5, 129.4, 129.2, 121.3, 121.1, 114.73, 114.66, 72.8,
72.5, 37.4, 36.6, 36.5, 35.8, 28.8, 28.2. IR (KBr): v = 2933, 2877,
1680, 1598, 1498 cm-1. HRMS (ESI-TOF) m/z [M+H]+ calcd
for C17H16ClO2S+: 319.0554, found: 319.0556.
2-(3-Chlorobenzoyl)-4-(phenoxymethyl)thietane
(3ag).
Yellow white solid 16 mg, 40% yield. M.p.: 68–72 °C. Rf = 0.41,
1
10% ethyl acetate in petroleum ether. Trans-isomer: H NMR
(400 MHz, CDCl3) (δ, ppm) = 7.82 (s, 1H, ArH), 7.69 – 7.62
(m, 1H, ArH), 7.55 – 7.50 (m, 1H, ArH), 7.42 – 7.38 (m, 1H,
ArH), 7.34 – 7.24 (m, 2H, ArH), 7.02 – 6.86 (m, 3H, ArH), 4.78
– 4.74 (m, 1H), 4.33 (dd, J = 9.8, 6.2 Hz, 1H), 4.26 – 4.21 (m,
1H), 4.04 – 3.93 (m, 1H), 3.69 (ddd, J = 12.6, 8.8, 5.5 Hz, 1H),
2.85 (ddd, J = 12.6, 8.5, 5.6 Hz, 1H). 13C {1H} NMR (101 MHz,
CDCl3) (δ, ppm) = 195.0, 194.8, 158.5, 158.4, 135.5, 135.24,
135.23, 133.5, 133.4, 130.1, 129.5, 129.4, 128.41, 128.38,
126.3, 121.3, 121.1, 114.75, 114.68, 72.8, 72.5, 37.4, 36.7, 36.5,
1
35.8, 28.9, 28.2. Cis-isomer: H NMR (400 MHz, CDCl3) (δ,
ppm) = 7.82 (s, 1H, ArH), 7.69 – 7.62 (m, 1H, ArH), 7.55 – 7.50
(m, 1H, ArH), 7.42 – 7.38 (m, 1H, ArH), 7.34 – 7.24 (m, 2H,
ArH), 7.02 – 6.86 (m, 3H, ArH), 4.78 – 4.74 (m, 1H), 4.26 –
4.21 (m, 1H), 4.10 (dd, J = 9.5, 7.3 Hz, 1H), 4.04 – 3.93 (m,
1H), 3.39 (ddd, J = 12.5, 6.1, 6.1 Hz, 1H), 3.14 (ddd, J = 12.9,
8.7, 8.7 Hz, 1H). 13C {1H} NMR (101 MHz, CDCl3) (δ, ppm) =
195.0, 194.8, 158.5, 158.4, 135.5, 135.24, 135.23, 133.5, 133.4,
130.1, 129.5, 129.4, 128.41, 128.38, 126.3, 121.3, 121.1, 114.75,
114.68, 72.8, 72.5, 37.4, 36.7, 36.5, 35.8, 28.9, 28.2. IR (KBr):
v = 2950, 2865, 1688, 1600, 1583, 1496 cm-1. HRMS (ESI-
TOF) m/z [M+H]+ calcd for C17H16ClO2S+: 319.0554, found:
319.0554.
2-(4-Bromobenzoyl)-4-(phenoxymethyl)thietane
(3ae).
White solid 21 mg, 47% yield. M.p.: 147–151 °C. Rf = 0.39, 10%
1
ethyl acetate in petroleum ether. Trans-isomer: H NMR (400
MHz, CDCl3) (δ, ppm) = 7.68 – 7.65 (m, 2H, ArH), 7.61 – 7.59
(m, 2H, ArH), 7.33 – 7.24 (m, 2H, ArH), 7.00 – 6.87 (m, 3H,
ArH), 4.77 – 4.74 (m, 1H), 4.32 (dd, J = 9.8, 6.2 Hz, 1H), 4.26
– 4.21 (m, 1H), 4.04 – 3.92 (m, 1H), 3.70 (ddd, J = 12.6, 8.8,
5.6 Hz, 1H), 2.84 (ddd, J = 12.7, 8.5, 5.6 Hz, 1H). 13C {1H}
NMR (101 MHz, CDCl3) (δ, ppm) = 195.3, 195.1, 158.5, 158.4,
132.6, 132.4, 132.2, 132.1, 129.8, 129.5, 129.4, 128.8, 128.7,
121.3, 121.1, 114.75, 114.69, 72.8, 72.5, 37.4, 36.6, 36.5, 35.8,
28.9, 28.2. Cis-isomer: 1H NMR (400 MHz, CDCl3) (δ, ppm) =
7.68 – 7.65 (m, 2H, ArH), 7.61 – 7.59 (m, 2H, ArH), 7.33 – 7.24
(m, 2H, ArH), 7.00 – 6.87 (m, 3H, ArH), 4.77 – 4.74 (m, 1H),
4.26 – 4.21 (m, 1H), 4.09 (dd, J = 9.5, 7.3 Hz, 1H), 4.04 – 3.92
(m, 1H), 3.39 (ddd, J = 12.6, 6.2, 6.2 Hz, 1H), 3.13 (ddd, J =
12.9, 8.6, 8.6 Hz, 1H). 13C {1H} NMR (101 MHz, CDCl3) (δ,
ppm) = 195.3, 195.1, 158.5, 158.4, 132.6, 132.4, 132.2, 132.1,
129.8, 129.5, 129.4, 128.8, 128.7, 121.3, 121.1, 114.75, 114.69,
2-(3,4-Dichlorobenzoyl)-4-(phenoxymethyl)thietane (3ah).
Golden yellow liquid 27 mg, 68% yield. Rf = 0.33, 10% ethyl
acetate in petroleum ether. Trans-isomer: 1H NMR (400 MHz,
CDCl3) (δ, ppm) = 7.86 – 7.76 (m, 1H, ArH), 7.53 – 7.49 (m,
1H, ArH), 7.47 – 7.44 (m, 1H, ArH), 7.28 – 7.14 (m, 2H, ArH),
6.94 – 6.77 (m, 3H, ArH), 4.66 – 4.61 (m, 1H), 4.24 (dd, J = 9.8,
6.1 Hz, 1H), 4.17 – 4.12 (m, 1H), 3.97 – 3.86 (m, 1H), 3.60 (ddd,
J = 12.7, 8.8, 5.4 Hz, 1H), 2.77 (ddd, J = 12.6, 8.5, 5.7 Hz, 1H).
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13C {1H} NMR (101 MHz, CDCl3) (δ, ppm) = 194.1, 193.8,
38.5, 38.4, 36.4, 35.9, 35.3, 35.1, 34.5, 29.1, 28.2, 27.9, 27.8.
IR (KBr): v = 2904, 2849, 1693, 1599, 1496, 1452, 1385 cm-1.
HRMS (ESI-TOF) m/z [M+H]+ calcd for C21H27O2S+:
343.1726, found: 343.1726.
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2
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158.4, 158.3, 138.1, 133.6, 133.5, 133.2, 130.9, 130.3, 130.2,
129.5, 129.4, 127.2, 121.3, 121.1, 114.7, 114.6, 72.7, 72.4, 37.2,
1
36.6, 36.5, 35.8, 28.8, 28.1. Cis-isomer: H NMR (400 MHz,
CDCl3) (δ, ppm) = 7.86 – 7.76 (m, 1H, ArH), 7.53 – 7.49 (m,
1H, ArH), 7.47 – 7.44 (m, 1H, ArH), 7.28 – 7.14 (m, 2H, ArH),
6.94 – 6.77 (m, 3H, ArH), 4.66 – 4.61 (m, 1H), 4.17 – 4.12 (m,
1H), 4.01 (dd, J = 9.4, 7.3 Hz, 1H), 3.97 – 3.86 (m, 1H), 3.31
(ddd, J = 12.4, 6.0, 6.0 Hz, 1H), 3.06 (dt, J = 12.9, 8.6 Hz, 8.6
Hz, 1H). 13C {1H} NMR (101 MHz, CDCl3) (δ, ppm) = 194.1,
193.8, 158.4, 158.3, 138.1, 133.6, 133.5, 133.2, 130.9, 130.3,
130.2, 129.5, 129.4, 127.2, 121.3, 121.1, 114.7, 114.6, 72.7,
72.4, 37.2, 36.6, 36.5, 35.8, 28.8, 28.1. IR (KBr): v = 2929, 2861,
1688, 1602, 1495 cm-1. HRMS (ESI-TOF) m/z [M+H]+ calcd
for C17H15Cl2O2S+: 353.0164, found: 353.0157.
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8
9
tert-Butyl 4-(phenoxymethyl)thietane-2-carboxylate (3ak).
Colorless liquid 14 mg, 40% yield. Rf = 0.55, 10% ethyl acetate
in petroleum ether. Trans-isomer: 1H NMR (400 MHz, CDCl3)
(δ, ppm) = 7.32 – 7.26 (m, 2H, ArH), 6.96 (t, J = 7.2 Hz, 1H,
ArH), 6.91 (d, J = 8.4 Hz, 2H, ArH), 4.23 (dd, J = 9.7, 6.9 Hz,
1H), 4.15 (dd, J = 9.6, 6.4 Hz, 1H), 3.98 – 3.93 (m, 2H), 3.32
(ddd, J = 12.5, 8.7, 5.7 Hz, 1H), 2.77 (ddd, J = 12.5, 8.8, 5.6 Hz,
1H), 1.49 (s, 9H). 13C {1H} NMR (101 MHz, CDCl3) (δ, ppm)
= 175.8, 172.4, 158.5, 132.2, 129.8, 129.5, 121.1, 114.7, 81.5,
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73.1, 72.7, 36.1, 35.7, 31.1, 27.9. Cis-isomer: H NMR (400
MHz, CDCl3) (δ, ppm) = 7.32 – 7.26 (m, 2H, ArH), 6.96 (t, J =
7.2 Hz, 1H, ArH), 6.92 – 6.88 (m, 2H, ArH), 4.27 (dd, J = 9.6,
7.0 Hz, 1H), 4.17 – 4.13 (m, 1H), 4.00 – 3.84 (m, 2H), 3.08 (ddd,
J = 12.5, 8.7, 8.7 Hz, 1H), 2.77 (ddd, J = 12.9, 6.4, 6.4 Hz, 1H),
1.47 (s, 9H). 13C {1H} NMR (101 MHz, CDCl3) (δ, ppm) =
175.8, 172.4, 158.5, 132.2, 129.8, 129.5, 121.1, 114.7, 81.5,
73.1, 72.7, 36.1, 35.7, 31.1, 27.9. IR (KBr): v = 2978, 2935,
1726, 1600, 1497, 1392, 1368 cm-1. HRMS (ESI-TOF) m/z
[M+Na]+ calcd for C15H20NaO3S+: 303.1025, found: 303.1026.
2-(1-Naphthoyl)-4-(phenoxymethyl)thietane (3ai). Golden
yellow liquid 14 mg, 34% yield. Rf = 0.36, 10% ethyl acetate in
petroleum ether. Trans-isomer: 1H NMR (400 MHz, CDCl3) (δ,
ppm) = 8.80 – 8.76 (m, 1H, ArH), 7.97 (d, J = 8.2 Hz, 1H, ArH),
7.86 – 7.83 (m, 1H, ArH), 7.64 – 7.58 (m, 2H, ArH), 7.55 – 7.50
(m, 1H, ArH), 7.45 – 7.41 (m, 1H, ArH), 7.30 – 7.22 (m, 2H,
ArH), 6.97 – 6.86 (m, 3H, ArH), 4.97 – 4.93 (m, 1H), 4.31 (dd,
J = 9.7, 6.5 Hz, 1H), 4.27 – 4.20 (m, 1H), 4.01 – 3.91 (m, 1H),
3.70 (ddd, J = 12.6, 8.9, 5.7 Hz, 1H), 2.85 (ddd, J = 12.6, 8.5,
5.4 Hz, 1H). 13C {1H} NMR (101 MHz, CDCl3) (δ, ppm) =
199.7, 199.5, 158.55, 158.46, 134.1, 133.5, 133.4, 131.9, 130.9,
129.5, 129.4, 128.4, 128.3, 128.2, 127.9, 127.7, 126.6, 126.0,
124.2, 121.2, 121.1, 114.7, 73.0, 72.6, 40.7, 39.1, 35.9, 35.0,
29.7, 29.2. Cis-isomer: 1H NMR (400 MHz, CDCl3) (δ, ppm) =
8.80 – 8.76 (m, 1H, ArH), 7.97 (d, J = 8.2 Hz, 1H, ArH), 7.86 –
7.83 (m, 1H, ArH), 7.64 – 7.58 (m, 2H, ArH), 7.55 – 7.50 (m,
1H, ArH), 7.45 – 7.41 (m, 1H, ArH), 7.30 – 7.22 (m, 2H, ArH),
6.97 – 6.86 (m, 3H, ArH), 4.97 – 4.93 (m, 1H), 4.27 – 4.20 (m,
1H), 4.12 (dd, J = 9.5, 7.1 Hz, 1H), 4.01 – 3.91 (m, 1H), 3.39
(ddd, J = 12.8, 6.4, 6.4 Hz, 1H), 3.14 (ddd, J = 12.9, 8.7, 8.7 Hz,
1H). 13C {1H} NMR (101 MHz, CDCl3) (δ, ppm) = 199.7, 199.5,
158.55, 158.46, 134.1, 133.5, 133.4, 131.9, 130.9, 129.5, 129.4,
128.4, 128.3, 128.2, 127.9, 127.7, 126.6, 126.0, 124.2, 121.2,
121.1, 114.7, 73.0, 72.6, 40.7, 39.1, 35.9, 35.0, 29.7, 29.2. IR
(KBr): v = 2927, 2857, 1676, 1599, 1496 cm-1. HRMS (ESI-
TOF) m/z [M+H]+ calcd for C21H19O2S+: 335.1100, found:
335.1100.
tert-Butyl
4-((benzyloxy)methyl)thietane-2-carboxylate
(3tk). Colorless liquid 855 mg, 52% yield. Rf = 0.31, 10% ethyl
acetate in petroleum ether. Trans-isomer: 1H NMR (400 MHz,
CDCl3) (δ, ppm) = 7.38 – 7.25 (m, 5H, ArH), 4.56 (s, 2H), 3.86
(dd, J = 8.8, 5.5 Hz, 1H), 3.84 – 3.61 (m, 3H), 3.20 (ddd, J =
12.7, 8.6, 5.5 Hz, 1H), 2.65 (ddd, J = 12.6, 8.8, 5.7 Hz, 1H),
1.47 (s, 9H). 13C {1H} NMR (101 MHz, CDCl3) (δ, ppm) =
172.6, 172.3, 138.0, 128.35, 128.32, 127.7, 127.6, 81.3, 75.8,
75.1, 73.2, 73.1, 36.4, 36.0, 35.2, 31.1, 30.7, 27.9. Cis-isomer:
1
1H NMR (400 MHz, CDCl3) (δ, ppm) = H NMR (400 MHz,
CDCl3) (δ, ppm) = 7.38 – 7.25 (m, 5H, ArH), 4.53 (s, 2H), 3.95
(dd, J = 8.6, 6.8 Hz, 1H), 3.84 – 3.61 (m, 3H), 2.95 (ddd, J =
12.7, 8.3, 8.3 Hz, 1H), 2.87 (ddd, J = 12.7, 6.5, 6.5 Hz, 1H),
1.45 (s, 9H). 13C {1H} NMR (101 MHz, CDCl3) (δ, ppm) =
172.6, 172.3, 138.0, 128.35, 128.32, 127.7, 127.6, 81.3, 75.8,
75.1, 73.2, 73.1, 36.4, 36.0, 35.2, 31.1, 30.7, 27.9. IR (KBr): v
= 2979, 2937, 2859, 1727, 1496, 1477, 1392, 1368, 737, 699
cm-1. HRMS (ESI-TOF) m/z [M+H]+ calcd for C16H23O3S+:
295.1362, found: 295.1356.
(Adamantan-1-yl)(4-(phenoxymethyl)thietan-2-
Synthesis of Sulfone 725
yl)methanone (3aj). Colorless liquid 30 mg, 70% yield. Rf =
1
0.63, 10% ethyl acetate in petroleum ether. Trans-isomer: H
To a performic acid solution, prepared by mixing and stirring
30% H2O2 (0.27 mL, 2.4 mmol) and 88% HCO2H (2.4 mL) at
r.t. for 0.5 h in an ice bath, was added dropwise the thietane 3tk
(118 mg, 0.4 mmol) obtained from the above step at 0 °C over
a period of 10 min. The resulting mixture was stirred and
allowed to warm to r.t. for 0.5–1 h. The resulting mixture was
washed with H2O. The organic phase was dried over anhydrous
Na2SO4 and concentrated in vacuo. The residue was purified by
column chromatography to give the sulfone 7.
NMR (400 MHz, CDCl3) (δ, ppm) = 7.33 – 7.23 (m, 2H, ArH),
7.01 – 6.84 (m, 3H, ArH), 4.40 (dd, J = 8.4, 5.4 Hz, 1H), 4.27 –
4.22 (m, 1H), 4.18 – 4.08 (m, 1H), 3.96 – 3.84 (m, 1H), 3.47
(ddd, J = 12.4, 8.7, 5.4 Hz, 1H), 2.62 (ddd, J = 12.4, 8.4, 5.8 Hz,
1H), 2.13 – 1.63 (m, 15H). 13C {1H} NMR (101 MHz, CDCl3)
(δ, ppm) = 211.2, 158.5, 129.5, 129.4, 121.1, 121.0, 114.69,
114.66, 73.0, 72.7, 46.4, 38.5, 38.4, 36.4, 35.9, 35.3, 35.1, 34.5,
29.1, 28.2, 27.9, 27.8. Cis-isomer: 1H NMR (400 MHz, CDCl3)
(δ, ppm) = 7.33 – 7.23 (m, 2H, ArH), 7.01 – 6.84 (m, 3H, ArH),
4.44 (dd, J = 8.4, 6.2 Hz, 1H), 4.27 – 4.22 (m, 1H), 4.18 – 4.08
(m, 1H), 3.96 – 3.84 (m, 1H), 3.18 (ddd, J = 12.6, 6.2, 6.2 Hz,
1H), 2.90 (ddd, J = 12.7, 8.7, 8.7 Hz, 1H), 2.13 – 1.63 (m, 15H).
13C {1H} NMR (101 MHz, CDCl3) (δ, ppm) = 211.2, 158.5,
129.5, 129.4, 121.1, 121.0, 114.69, 114.66, 73.0, 72.7, 46.4,
tert-Butyl 4-((benzyloxy)methyl)thietane-2-carboxylate 1,1-
dioxide (7). Colorless liquid 70 mg, 40% yield. Rf = 0.24, 10%
1
ethyl acetate in petroleum ether. Trans-isomer: H NMR (400
MHz, CDCl3) (δ, ppm) = 7.39 – 7.27 (m, 5H, ArH), 4.85 (ddd,
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J = 10.0, 5.8, 1.2 Hz, 1H), 4.64 – 4.54 (m, 3H), 3.91 (dd, J = (101 MHz, CDCl3) (δ, ppm) = 195.1, 139.5, 134.3, 130.0, 128.9,
1
2
3
4
5
6
7
8
10.8, 7.5 Hz, 1H), 3.91 (dd, J = 10.8, 4.6 Hz, 1H), 2.59 (ddd, J
= 12.2, 10.4, 5.8 Hz, 1H), 1.99 (ddd, J = 12.2, 10.1, 6.9 Hz, 1H),
1.51 (s, 9H). 13C {1H} NMR (101 MHz, CDCl3) (δ, ppm) =
163.2, 137.2, 128.4, 127.9, 127.8, 83.9, 79.0, 77.7, 73.4, 66.3,
27.9, 14.2. IR (KBr): v = 2981, 2935, 2867, 1732, 1497, 1455,
1394, 1370, 1336, 1150, 739, 700 cm-1. HRMS (ESI-TOF) m/z
[M+Na]+ calcd for C16H22NaO5S+: 349.1080, found: 349.1080.
49.3, 34.0, 31.2, 31.1, 29.7. IR (KBr): v = 2930, 2859, 1689,
1594, 1463 cm-1. HRMS (ESI-TOF) m/z [M+H]+ calcd for
C11H12ClOS+: 227.0292, found: 227.0292.
2-(4-Bromobenzoyl)tetrahydrothiophene (5e). White solid
25 mg, 74% yield. M.p.: 76–79 °C. Rf = 0.33, 10% ethyl acetate
in petroleum ether. 1H NMR (400 MHz, CDCl3) (δ, ppm) = 7.80
(d, J = 8.2 Hz, 2H, ArH), 7.60 (d, J = 8.2 Hz, 2H, ArH), 4.66
(dd, J = 7.1, 4.2 Hz, 1H), 2.98 – 2.88 (m, 2H), 2.64 – 2.57 (m,
1H), 2.27 – 2.10 (m, 2H), 2.02 – 1.93 (m, 1H). 13C {1H} NMR
(101 MHz, CDCl3) (δ, ppm) = 195.1, 139.5, 134.3, 130.0, 128.9,
49.3, 34.0, 31.2, 31.1, 29.7. IR (KBr): v = 2934, 2867, 1685,
1592 cm-1. HRMS (ESI-TOF) m/z [M+H]+ calcd for
C11H12BrOS+: 270.9787, found: 270.9787.
General
Procedure
for
the
Synthesis
of
9
Tetrahydrothiophenes 5
10
11
12
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14
15
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Conditions C:
A pressure tube was charged with
[Ir(COD)Cl]2 (4 mg, 5 mol %), thietane (0.125 mmol),
sulfoxonium ylide (0.25 mmol), and DCE (1 mL). The reaction
mixture was stirred under N2 conditions at 80 °C in an oil bath
for 4 h. After removal of solvent under reduced pressure, the
residue was purified by silica gel chromatography with a
mixture of petroleum ether and ethyl acetate (10:1, v/v) as eluent
to afford product 5.
Gram Scale Synthesis of Thietane 3aa
A pressure tube was charged with [Rh(COD)Cl]2 (123 mg,
2.5 mmol, 5 mol %), C(CH2OH)4 (136 mg, 10 mmol, 20 mol%),
thiirane 1a (0.83g, 5 mmol), sulfoxonium ylide 2a (1.80g, 10
mmol), and DCE (30 mL). The reaction mixture was stirred
under N2 conditions at 80 °C in an oil bath for 6 h. After removal
of solvent under reduced pressure, the residue was purified by
silica gel chromatography using PE/EA (10:1, v/v) as eluent to
afford the product 3aa (0.82g, 58%).
2-Benzoyltetrahydrothiophene (5a). Colorless liquid 13 mg,
1
55% yield. Rf = 0.42, 10% ethyl acetate in petroleum ether. H
NMR (400 MHz, CDCl3) (δ, ppm) = 7.98 – 7.92 (m, 2H, ArH),
7.60 – 7.53 (m, 1H, ArH), 7.50 – 7.43 (m, 2H, ArH), 4.74 (dd,
J = 7.0, 4.2 Hz, 1H), 3.01 – 2.87 (m, 2H), 2.68 – 2.57 (m, 1H),
2.66 – 2.58 (m, 1H), 2.29 – 2.10 (m, 2H), 1.99 (dddd, J = 12.8,
8.6, 7.1, 5.9 Hz, 1H). 13C {1H} NMR (101 MHz, CDCl3) (δ,
ppm) = 196.4, 135.9, 133.1, 128.6, 49.3, 33.9, 31.3, 31.1. IR
(KBr): v = 2930, 2874, 1687, 1599, 1452 cm-1. HRMS (ESI-
TOF) m/z [M+H]+ calcd for C11H13OS+: 193.0682, found:
193.0682.
Gram Scale Synthesis of Thietane 3tk
A pressure tube was charged with [Rh(COD)Cl]2 (137 mg,
0.28 mmol, 5 mol %), C(CH2OH)4 (151 mg, 1.11 mmol, 20
mol%), thiirane 1t (1g, 5.59 mmol), sulfoxonium ylide 2k
(1.96g, 10 mmol), and DCE (30 mL). The reaction mixture was
stirred under N2 conditions at 80 °C in an oil bath for 7 h. After
removal of solvent under reduced pressure, the residue was
purified by silica gel chromatography using PE/EA (10:1, v/v)
as eluent to afford the product 3tk (0.86g, 52%).
2-(4-Methylbenzoyl)tetrahydrothiophene (5b). White solid
17 mg, 66% yield. M.p.: 72–74 °C. Rf = 0.33, 10% ethyl acetate
in petroleum ether. 1H NMR (400 MHz, CDCl3) (δ, ppm) = 7.84
(d, J = 7.9 Hz, 2H, ArH), 7.26 (d, J = 8.1 Hz, 1H, ArH), 4.71
(dd, J = 7.1, 4.4 Hz, 1H), 2.98 – 2.87 (m, 2H), 2.64 – 2.56 (m,
1H), 2.41 (s, 3H), 2.28 – 2.09 (m, 2H), 2.01 – 1.93 (m, 1H). 13
C
ASSOCIATED CONTENT
Supporting Information
{1H} NMR (101 MHz, CDCl3) (δ, ppm) = 196.1, 143.9, 133.4,
129.3, 128.7, 49.3, 33.9, 31.3, 31.2, 21.6. IR (KBr): v = 2961,
2934, 2865, 1683, 1608, 1443 cm-1. HRMS (ESI-TOF) m/z
[M+H]+ calcd for C12H15OS+: 207.0838, found: 207.0838.
The Supporting Information is available free of charge on the ACS
Publications website at DOI:
Copies of 1H and 13C {1H} NMR spectra for all sulfur ylides and
products, and copies of NMR spectra and GC-MS profiles on
mechanistic investigations (PDF)
2-(4-Methoxylbenzoyl)tetrahydrothiophene (5c). White
solid 14 mg, 50% yield. M.p.: 79–81 °C. Rf = 0.30, 10% ethyl
acetate in petroleum ether. 1H NMR (400 MHz, CDCl3) (δ, ppm)
= 7.93 (d, J = 8.8 Hz, 2H, ArH), 6.94 (d, J = 8.8 Hz, 2H, ArH),
4.69 (dd, J = 7.3, 4.8 Hz, 1H), 3.86 (s, 3H), 2.98 – 2.87 (m, 2H),
2.63 – 2.56 (m, 1H), 2.29 – 2.09 (m, 2H), 2.01 – 1.92 (m, 1H).
13C {1H} NMR (101 MHz, CDCl3) (δ, ppm) = 195.2, 163.5,
130.8, 128.9, 113.8, 55.5, 49.1, 33.9, 31.4, 31.2. IR (KBr): v =
2964, 2934, 2862, 1678, 1602, 1511, 1454 cm-1. HRMS (ESI-
TOF) m/z [M+H]+ calcd for C12H15O2S+: 223.0787, found:
223.0787.
AUTHOR INFORMATION
Corresponding Author
* E-mail: jxxu@mail.buct.edu.cn.
ORCID
Jiaxi Xu: 0000-0002-9039-4933;
Jun Dong: 0000-0002-0358-5505.
Notes
The authors declare no competing financial interest.
2-(4-Chlorobenzoyl)tetrahydrothiophene (5d). Yellow solid
19 mg, 68% yield. M.p.: 54–56 °C. Rf = 0.33, 10% ethyl acetate
in petroleum ether. 1H NMR (400 MHz, CDCl3) (δ, ppm) = 7.88
(d, J = 8.3 Hz, 2H, ArH), 7.43 (d, J = 8.3 Hz, 2H, ArH), 4.67
(dd, J = 7.1, 4.3 Hz, 1H), 2.98 – 2.88 (m, 2H), 2.64 – 2.57 (m,
1H), 2.27 – 2.10 (m, 2H), 2.02 – 1.94 (m, 1H). 13C {1H} NMR
ACKNOWLEDGMENT
This work was supported by the National Natural Science
Foundation of China (Nos. 21572017 and 21772010) and the
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The Journal of Organic Chemistry
Fundamental Research Funds for the Central Universities
(XK1802-6).
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Reactions of Sulfoxonium Ylides with 2-Amino Heterocycles.
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(t, J = 7.6 Hz, 2H), 5.75(s, 1H), 3.92 – 3.82 (m, 1H), 3.43 (dd,
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